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| United States Patent |
6,165,970
|
|
|
December 26, 2000
|
Detergent composition comprising acrylic acid-based polymer and amino
tricarboxylic acid-based compound
Abstract
There is provided a detergent composition comprising (a) an organic polymer
containing acrylic acid or its salts, having an average molecular weight
of less than 15,000; and (b) an amino tricarboxylic acid or its salts or
complexes or any mixture thereof exhibiting improved soil and stain
removal.
| Inventors:
|
Williams (nee Mac Beath); Fiona Susan (Newcastle upon Tyne, GB);
Kitko; David Jonathan (Cincinnati, OH);
Murata; Susumu (Osho-Nishi-machi, JP);
Tsunetsugu; Toshiko (Kobe, JP);
Tsunetsugu; Shuichi (Kobe, JP)
|
| Assignee:
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The Procter & Gamble Company (Cincinnati, OH)
|
| Appl. No.:
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155457 |
| Filed:
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February 23, 1999 |
| PCT Filed:
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March 25, 1997
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| PCT NO:
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PCT/US97/04925
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| 371 Date:
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February 23, 1999
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| 102(e) Date:
|
February 23, 1999
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| PCT PUB.NO.:
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WO97/36975 |
| PCT PUB. Date:
|
October 9, 1997 |
Foreign Application Priority Data
| Current U.S. Class: |
510/480; 510/223; 510/229; 510/230; 510/318; 510/361; 510/398; 510/434; 510/476; 510/533 |
| Intern'l Class: |
C11D 003/30; C11D 003/37 |
| Field of Search: |
510/223,229,230,318,361,398,434,476,480,533
|
References Cited
U.S. Patent Documents
| 3627686 | Dec., 1971 | Sabatelli et al. | 252/527.
|
| 3708436 | Jan., 1973 | Thompson et al. | 252/527.
|
| 4698174 | Oct., 1987 | Denzinger et al. | 252/174.
|
| 5597789 | Jan., 1997 | Sadlowski | 510/230.
|
| 5750483 | May., 1998 | Welch et al. | 510/230.
|
| 5759978 | Jun., 1998 | Welch et al. | 510/230.
|
| 5783524 | Jul., 1998 | Greindl et al. | 507/90.
|
Other References
Chemical Abstract HCAPLUS file accession No. 1981:409124, for JP 55-160099,
May 1979.
Chemical Abstract HCAPLUS file accession No. 1981:409123, for JP 55-157695,
Dec. 1980.
"New biodegradable complexing agents, Relations between structure and
degradability", by Potthoff-Karl Birgitt, in SOFW J. (1994), 120(2/3),
104, 106-9--see enclosed translation.
|
Primary Examiner: Gupta; Yogendra
Assistant Examiner: Boyer; Charles
Attorney, Agent or Firm: Hasse; Donald E., Echler; Richard S., Bolam; Brian M.
Claims
What is claimed is:
1. A cleaning compositions comprising:
a) from 0.005% to 20%, by weight, of an organic polymer which contains
acrylic acid, acrylic salts, or mixtures thereof, wherein said polymer has
an average molecular weight of 1,500 daltons to 12,000 daltons;
b) an amino tricarboxylic acid or salt thereof having the formula:
##STR25##
wherein R.sub.1, R.sub.2 and R.sub.3 are each C.sub.1 -C.sub.4 alkylene; X
is selected from the group consisting of alkyl, aryl, alkenyl, alkaryl,
amino, hydroxyl, amido, or mixtures thereof; n is 0 or 1; provided the
ratio of said organic polymer (a) to said tricarboxylic acid is from 20:1
to 2:1; and
c) the balance carriers and adjunct ingredients.
2. A composition according to claim 1 wherein said organic polymer has an
average molecular weight of from 2500 daltons to 9000 daltons.
3. A composition according to claim 2 wherein said organic polymer
comprises:
i) from 60% to 80% by weight, of acrylic acid; and
ii) from 40% to 20% by weight, of methyl acrylic acid.
4. A composition according to claim 3 wherein said co-polymer has an
average molecular weight of 3500 daltons.
5. A composition according to claim 3 further comprising from 0.0001% to 4%
by weight, of an enzyme selected from the group consisting of lipase,
amylase, protease, esterase, cellulase, pectinase, lactase, peroxidase
enzyme, and mixtures thereof.
6. A cleaning composition comprising:
a) from 0.005% to 20% by weight, of an organic polymer which contains
acrylic acid, acrylic acid salts, or mixtures thereof, wherein said
polymer has an average molecular weight of less than 15,000 daltons;
b) an amino tricarboxylic acid or salt thereof having the formula:
##STR26##
wherein R.sub.1, R.sub.2, and R.sub.3 are each C.sub.1 -C.sub.4 alkylene;
X is selected from the group consisting of alky, aryl, alkenyl, alkaryl,
amino, hydroxyl, amido, or mixtures thereof; n is 0 or 1; provided the
ratio of said organic polymer in (a) to tricarboxylic acid is from 50:1 to
1:5;
c) from 1.5% to 60% by weight, of a hydrophobic bleaching system, said
bleaching system comprising:
i) from 5% to 98.75% by weight, of a perbydrate salt selected from the
group consisting of perborate, percarbonate, perphosphate, persilicate,
and mixtures thereof; wherein said perhydrate salt comprises from 1% to
40% by weight, of said laundry composition;
ii) from 1.25% to 95% by weight, of a peroxyacid bleach precursor, wherein
said precursor comprises from 0.5% to 20% by weight, of said laundry
composition; and
d) the balance carriers and adjunct ingredients.
7. A composition according to claim 6 wherein said peroxygen bleach
precursor has the formula:
##STR27##
wherein L is a leaving group, R.sup.1 is C.sub.1 -C.sub.14 aryl, C.sub.1
-C.sub.14 alkaryl, and mixtures thereof; R.sup.2 is C.sub.1 -C.sub.14
alkylene, C.sub.1 -C.sub.14 arylene, C.sub.1 -C.sub.14 alkarylene, and
mixtures thereof; R.sup.5 is C.sub.1 -C.sub.10 alkyl, C.sub.1 -C.sub.10
aryl, C.sub.1 -C.sub.10 alkaryl, and mixtures thereof; provided when taken
together R.sup.1 and R.sup.5 do not comprise more than 18 carbon atoms.
8. A composition according to claim 6 wherein said bleach precursor is
selected from the group consisting of
(6-octanamido-caproyl)oxybenzenesulfonate, (6-decanamido-caproyl)
oxybenzenesulfonate, (6-nonanamidocaproyl)oxybenzenesulfonate, and
mixtures thereof.
9. A composition according to claim 6 wherein said perhydrate salt is
sodium perborate, sodium percarbonate, and mixtures thereof.
10. A composition according to claim 6 comprising from 5% to 25% by weight,
of said composition said perhydrate salt.
Description
TECHNICAL FIELD
The present invention relates to detergent compositions, useful in a
cleaning method, containing in combination, a low molecular weight polymer
containing acrylic acid and an amino tricarboxylic acid chelant,
exhibiting improved soil and stain removal.
BACKGROUND OF THE INVENTION
Detergent compositions designed for use in cleaning, particularly automatic
dishwashing and laundry methods are well known, and a consistent effort
has been made by detergent manufact urers to improve the cleaning and/or
rinsing efficiency of said compositions as reflected by numerous patent
publications.
The general problem of the formation of deposits as spots and films on the
articles in the wash, and on the dishwasher and washing machine parts is
well known in the art.
Whilst the general problem of deposit formation is known, a full
understanding of the many facets of the problem is however still an active
area of research.
A range of deposit types can be encountered. The redeposition of soils or
the breakdown products thereof, which have previously been removed from
the soiled tableware in the washload, provides one deposit type. Insoluble
salts such as calcium carbonate, calcium fatty acid salts (lime soaps), or
certain silicate salts are other common deposit types. Composite deposit
types are also common. Indeed, once an initial minor deposit forms it can
act as a "seeding centre" for the build up of a larger, possibly
composite, deposit structure.
Deposit formation can occur on a range of commonly encountered substrate
surfaces including a range of fabric types, plastic, glass, metal and
china surfaces. Certain deposit types however, show a greater propensity
to deposit on certain substrates. For example, lime soap deposit formation
tends to be a particular problem on plastic substrates, and silicate
deposit formation tends to occur on glassware.
The formation of insoluble carbonate, especially calcium carbonate,
deposits is a particular problem. There is a general appreciation in the
art, as represented for example by EP-A-364,067 in the name of Clorox,
CH-A-673,033 in the name of Cosmina, and EP-A-551,670 in the name of
Unilever, that calcium carbonate deposit formation is a particular problem
when non-phosphate containing detergent formulations are employed. In
general, this can be explained by the slightly inferior builder capacity
of the typically employed non-phosphate builder systems in comparison to
phosphate builder formulations. The problem of calcium carbonate deposit
formation is understood to be especially apparent when these formulations
contain a carbonate builder component, as for example is essential to the
compositions taught by EP-A-364,067.
The Applicants have now found that the problem of CaCO.sub.3 deposit
formation can exist even in the absence of a carbonate builder component
in the machine dishwashing and laundry detergent formulations, and
especially when that formulation contains no phosphate builder component.
The naturally sourced, inlet water to washing machines can be a sufficient
source of Ca.sup.2+ and Mg.sup.2+ ions and HCO.sub.3- /CO.sub.3.sup.2-
ions to make deposit formation a problem. Whilst the salt softening
system, through which the inlet water will pass prior to entry into the
main cavity of the dishwasher machine, can be efficient at removing the
naturally present Ca.sup.2+ and Mg.sup.2+ ions it is inefficient at
removing the HCO.sub.3- /CO.sub.3.sup.2- ions which therefore enter into
the wash/rinse solution.
The Applicants have now established that both the levels of Ca.sup.2+
/Mg.sup.2+ hardness ions and the levels of HCO.sub.3- /CO.sub.3.sup.2-
ions in the wash/rinse water of the dishwasher machine are factors
controlling calcium carbonate deposit formation. Critical levels of both
components must be exceeded for carbonate-related deposit formation to
occur. These critical levels are to an extent interdependent. Thus, even
in wash solutions containing high levels of one component deposit
formation will not occur in the absence of the critical level of the other
component.
A relatively high level of Ca.sup.2+ ions in the wash solution can be
desirable for the effective performance of certain enzyme components of
the detergent formulation, particularly lipolytic and proteolytic enzymes.
Such higher levels of Ca.sup.2+ tend to be present when non-phosphate
built formulations are employed. Whilst these relatively high levels of
Ca.sup.2+ are desirable for enzyme performance, calcium carbonate
deposition will tend to occur if the solution contains a level of
carbonate ion above the critical limit for deposit formation.
The Applicants have also established that the formation of deposit "seeding
centres", which in turn enable the build up of more substantial deposits,
occurs most commonly in the rinse cycle of the dishwasher machine. Deposit
build up is most apparent on the heater element of the dishwasher machine.
It has also been established that the problem is most apparent when more
alkaline formulations, such as those of pH of 9.8 and above, are employed.
An upper limit to the pH of about 11.5 has been found to be preferred for
the effective working of other preferred components of the composition
such as peroxyacid bleaches and enzymes.
The Applicants have found that the problem of calcium carbonate deposit
formation may be effectively ameliorated by the inclusion of an amino
tricarboxylic acid (ATCA) component in combination with an acrylic acid
containing polymer having a molecular weight of less than 15,000 into the
detergent formulation.
In an automatic dishwashing context, it has been found that acrylic acid
containing organic polymers of higher molecular weight, such as the
commonly used maleic/acrylic acid copolymers of molecular weight from
typically 40,000 to 80,000, did not provide equivalent deposit formation
prevention capability. Indeed, the formation of the insoluble calcium
salts of such higher molecular weight polymers was noted in certain
circumstances potentially to lead to a worsening of the deposition profile
of the compositions in use.
When the combination of said amino carboxylic acid and polymer components
is employed in a non-phosphate built formulation the occurrence of calcium
carbonate deposits is essentially comparable to that obtained for a more
highly built, phosphate containing formulation which does not contain
these components.
The Applicants have also found that carboxylates and polycarboxylates,
particularly citrates, are especially useful components of the
compositions of the invention because of their magnesium binding capacity
which tends to prevent the formation of insoluble magnesium salts, such as
magnesium silicate on the articles in the wash. Such polycarboxylates also
provide calcium binding capacity to the compositions, thus contributing
further to the prevention of the formation of calcium salt deposits.
The Applicants have also found that the more effective control of calcium
carbonate deposition can also lead to benefits in the prevention of the
formation of other deposit types, particularly lime soap deposits and
silicate deposits.
Lime soap deposits are most commonly encountered when the washload contains
fatty soils, which naturally contain levels of free fatty acids, and when
lipolytic enzymes are components of the formulation. Lipolytic enzymes
catalyse the degradation of fatty soils into free fatty acids and
glycerol. Silicate is a common component of machine dishwashing
formulations, where it is added for its china and glass care capability.
It is the Applicant's finding that by preventing the formation of calcium
carbonate deposit "seeding centres", most particularly in the rinse cycle,
the build up of other deposit types from these "seeding centres" is also
prevented.
SUMMARY OF THE INVENTION
According to the present invention there is provided a detergent
composition containing in combination
(a) an organic polymer containing acrylic acid or its salts, having an
average molecular weight of less than 15,000; and
(b) an amino tricarboxylic acid or salt thereof wherein said amino
tricarboxylic acid has the general formula:
##STR1##
where R.sub.1, R.sub.2 and R.sub.3 are alkyl groups or substituted alkyl
groups of chain length C1 to C4; n is O or 1; and
X is an organic substituent group.
DETAILED DESCRIPTION OF THE INVENTION
Low Molecular Weight Acrylic Acid Containing Organic Polymer
The first component of the detergent compositions in accord with the
invention is an organic polymer containing acrylic acid or its salts
having an average molecular weight of less than 15,000, hereinafter
referred to as low molecular weight acrylic acid containing polymer.
The low molecular weight acrylic acid containing polymer has an average
molecular weight of less than 15,000, preferably from 500 to 12,000, more
preferably from 1,500 to 10,000, most preferably from 2,500 to 9,000.
The low molecular weight acrylic acid containing organic polymer is
preferably present at a level of from 0.005% to 20%, more preferably from
0.1 % to 10%, most preferably from 0.2% to 8% by weight of the
compositions.
The weight ratio of low molecular weight acrylic acid containing polymer to
ATCA component is preferably from 50:1 to 1:5, more preferably from 20:1
to 2:1, most preferably from 15:1 to 1:1.
In a preferred aspect, the low molecular weight acrylic containing polymer
and ATCA components are present in the compositions in intimate admixture,
most especially in the form of a particle, such as one made by a
spray-drying or agglomeration process, comprising said two components
which itself forms part of a granular composition.
The low molecular weight acrylic acid containing polymer may be either a
homopolymer or a copolymer including the essential acrylic acid or acrylic
acid salt monomer units. Copolymers may include essentially any suitable
other monomer units including modified acrylic, fumaric, maleic, itaconic,
aconitic, mesaconic, citraconic, and methylenemalonic acid or their salts,
maleic anhydride, acrylamide, alkylene, vinylmethyl ether, styrene and any
mixtures thereof.
Preferred commercially available low molecular weight acrylic acid
containing homopolymers include those sold under the tradename Sokalan
PA30, PA20, PA15 and PA10 by BASF GmbH, and those sold under the tradename
Acusol 45N by Rohm and Haas.
Preferred low molecular weight acrylic acid containing copolymers include
those which contain as monomer units: a) from 90% to 10%, preferably from
80 % to 20 % by weight acrylic acid or its salts and b) from 10% to 90%,
preferably from 20% to 80% by weight of a substituted acrylic monomer or
its salts having the general formula--[CR.sub.2 --CR.sub.1 (CO--O--R.sub.3
]--wherein at least one of the substituents R.sub.1, R.sub.2 or R.sub.3,
preferably R.sub.1 or R.sub.2 is a 1 to 4 carbon alkyl or hydroxyalkyl
group, R.sub.1 or R.sub.2 can be a hydrogen and R.sub.3 can be a hydrogen
or alkali metal salt. Most preferred is a substituted acrylic monomer
wherein R.sub.1 is methyl, R.sub.2 is hydrogen (i.e. a methyl acrylic acid
monomer). The most preferred copolymer of this type has a molecular weight
of 3500 and contains 60% to 80% by weight of acrylic acid and 40% to 20%
by weight of methyl acrylic acid.
Preferred commercially available low molecular weight acrylic acid
containing copolymers include those sold under the tradename Sokalan CP10
by BASF GmbH.
Other suitable polyacrylate/modified polyacrylate copolymers include those
copolymers of saturated aliphatic carboxylic acids disclosed in U.S. Pat.
Nos. 4,530,766 and 5,084,535 which have a molecular weight of less than
15,000 in accordance with the invention.
Amino Tricarboxylic Acid (ATCA)
An essential component of the detergent compositions in accordance with the
invention is an amino tricarboxylic acid (ATCA) or one of its
salts/complexes with the low molecular weight polymer to inhibit build up
and growth of undesirable deposits. It is believed that it particularly
acts as to inhibit growth of calcium carbonate deposits. The ATCA is
selected from the group having the general formula:
##STR2##
where R.sub.1, R.sub.2 or R.sub.3 are an alkyl group or substituted alkyl
group of chain length C1 to C4. X is an organic substitutent group, that
is a substituent typically encountered in organic compounds, but excluding
X being a hydrogen substituent. X can thus for example be an alkyl, aryl,
alkenyl or alkaryl group optionally substituted by any functionality
including for example, amino, hydroxyl, amide and ether functionalities. X
may also be an organic functional group including for example an amine,
hydroxyl, amide, ester or ether group. X is preferably an alkyl group,
most preferably a methyl or ethyl group. ATCA is preferably methyl glycine
diacetic acid that is where R.sub.1 =R.sub.2 =a--CH.sub.2 --group and
X=CH.sub.3.
The ATCA component may be present in its acid form or in the form of one of
its salts or complexes with a suitable counter cation and reference
hereinafter to the acid implicitly includes reference to said salts or
complexes. Preferably any salts/complexes are water soluble, with the
alkali metal and alkaline earth metal salts/complexes being especially
preferred.
Optional Detergent Components
The detergent composition may optionally contain various components
including surfactants, bleaching agents, alkalinity sources, water-soluble
builder compounds, lime soap dispersants, additional organic polymeric
compounds including polymeric dye transfer inhibiting agents, crystal
growth inhibitors, heavy metal ion sequestrants, enzymes and enzyme
stabilisers, corrosion inhibitors, suds suppressors, solvents, fabric
softening agents, optical brighteners and hydrotropes.
Additional Organic Polymeric Compound
Certain additional organic polymeric compounds may be added to the
detergent compositions of the invention, however, in certain cases their
presence is desirably minimised. By additional organic polymeric compounds
it is meant essentially any polymeric organic compounds commonly used as
dispersants, anti-redeposition and soil suspension agents in detergent
compositions, which do not fall within the definition of low molecular
weight acrylic acid containing polymers given hereinbefore.
Additional organic polymeric compound may by incorporated into the
detergent compositions of the invention at a level of from 0.05% to 30%,
preferably from 0.5% to 15%, most preferably from 1% to 10% by weight of
the compositions.
Examples of additional organic polymeric compounds whose presence is
desirably minimised, and which are preferably not present, include the
water soluble organic homo- or co-polymeric polycarboxylic acids or their
salts in which the polycarboxylic acid comprises at least two carboxyl
radicals separated from each other by not more than two carbon atoms.
Polymers of the latter type are disclosed in GA-A-1,596,756. Examples of
such salts are the co-polymers of polyacrylate with maleic anhydride
having a molecular weight of from 20,000 to 150,000, especially about
40,000 to 80,000.
The polyamino compounds are useful herein including those derived from
aspartic acid such as those disclosed in EP-A-305,282, EP-A-305,283 and
EP-A-351,629.
Other additional organic polymeric compounds suitable for incorporation in
the detergent compositions herein include cellulose derivatives such as
methylcellulose, carboxymethylcellulose and hydroxyethylcellulose.
Further useful additional organic polymeric compounds are the polyethylene
glycols, particularly those of molecular weight 1000-10000, more
particularly 2000 to 8000 and most preferably about 4000.
Surfactant
A highly preferred component of the compositions used in this invention is
a surfactant system comprising surfactant selected from anionic, cationic,
nonionic ampholytic and zwitterionic surfactants and mixtures thereof.
Automatic dishwashing machine products should be low foaming in character
and thus the foaming of the surfactant system must be suppressed or more
preferably be low foaming, typically nonionic in character. The surfactant
system is typically present at a level of from 0.2% to 30% by weight, more
preferably from 0.5% to 10% by weight, most preferably from 1% to 5% by
weight of the compositions.
A typical listing of anionic, nonionic, ampholytic and zwitterionic
classes, and species of these surfactants, is given in U.S. Pat. No.
3,929,678 issued to Laughlin and Heuring on Dec. 30, 1975. A list of
suitable cationic surfactants is given in U.S. Pat. No. 4,259,217 issued
to Murphy on Mar. 31, 1981. A listing of surfactants typically included in
automatic dishwashing detergent compositions is given for example, in
EP-A-0414 549 and PCT Applications Nos. WO 93/08876 and WO 93/08874.
Nonionic Surfactant
Essentially any nonionic surfactants useful for detersive purposes can be
included in the compositions. Preferred, non-limiting classes of useful
nonionic surfactants are listed below.
Nonionic Ethoxylated Alcohol Surfactant
The alkyl ethoxylate condensation products of aliphatic alcohols with from
about 1 to about 25 moles of ethylene oxide are suitable for use herein.
The alkyl chain of the aliphatic alcohol can either be straight or
branched, primary or secondary, and generally contains from 6 to 22 carbon
atoms. Particularly preferred are the condensation products of alcohols
having an alkyl group containing from 8 to 20 carbon atoms with from about
2 to about 10 moles of ethylene oxide per mole of alcohol.
Nonionic Ethoxylated/propoxylated Fatty Alcohol Surfactant
The ethoxylated C.sub.6 -C.sub.18 fatty alcohols and C.sub.6 -C.sub.18
mixed ethoxylated/propoxylated fatty alcohols are suitable surfactants for
use herein, particularly where water soluble. Preferably the ethoxylated
fatty alcohols are the C.sub.10 -C.sub.18 ethoxylated fatty alcohols with
a degree of ethoxylation of from 3 to 50, most preferably these are the
C.sub.12 -C.sub.18 ethoxylated fatty alcohols with a degree of
ethoxylation from 3 to 40. Preferably the mixed ethoxylatedlpropoxylated
fatty alcohols have an alkyl chain length of from 10 to 18 carbon atoms, a
degree of ethoxylation of from 3 to 30 and a degree of propoxylation of
from 1 to 10.
Nonionic EO/PO Condensates With Propylene Glycol
The condensation products of ethylene oxide with a hydrophobic base formed
by the condensation of propylene oxide with propylene glycol are suitable
for use herein. The hydrophobic portion of these compounds preferably has
a molecular weight of from about 1500 to about 1800 and exhibits water
insolubility. Examples of compounds of this type include certain of the
commercially-available Pluronic.TM. surfactants, marketed by BASF.
Nonionic EO Condensation Products With Propylene Oxide/ethylene Diamine
Adducts
The condensat ion p roducts of ethylene oxide with the product resulting
from the reaction of propylene oxide and ethylenediamine are suitable for
use herein. The hydrophobic moiety of these products consists of the
reaction product of ethylenediamine and excess propylene oxide, and
generally has a molecular weight of from about 2500 to about 3000.
Examples of this type of nonionic surfactant include certain of the
commercially available Tetronic.TM. compounds, marketed by BASF.
Anionic Surfactant
Essentially any anionic surfactants useful for detersive purposes are
suitable. These can include salts (including, for example, sodium,
potassium, ammonium, and substituted ammonium salts such as mono-, di- and
triethanolamine salts) of the anionic sulfate, sulfonate, carboxylate and
sarcosinate surfactants. Anionic sulfate surfactants are preferred.
Other anionic surfactants include the isethionates such as the acyl
isethionates, N-acyl taurates, fatty acid amides of methyl tauride, alkyl
succinates and sulfosuccinates, monoesters of sulfosuccinate (especially
saturated and unsaturated C.sub.12 -C.sub.18 monoesters) diesters of
sulfosuccinate (especially saturated and unsaturated C.sub.6 -C.sub.14
diesters), N-acyl sarcosinates Resin acids and hydrogenated resin acids
are also suitable, such as rosin, hydrogenated rosin, and resin acids and
hydrogenated resin acids present in or derived from tallow oil.
Anionic Sulfate Surfactant
Anionic sulfate surfactants suitable for use herein include the linear and
branched primary and secondary alkyl sulfates, alkyl ethoxysulfates, fatty
oleoyl glycerol sulfates, alkyl phenol ethylene oxide ether sulfates, the
C.sub.5 -C.sub.17 acyl--N--(C.sub.1 -C.sub.4 alkyl) and --N--(C.sub.1
-C.sub.2 hydroxyalkyl) glucamine sulfates, and sulfates of
alkylpolysaccharides such as the sulfates of alkylpolyglucoside (the
nonionic nonsulfated compounds being described herein).
Alkyl sulfate surfactants are preferably selected from the linear and
branched primary C.sub.10 -C.sub.18 alkyl sulfates, more preferably the
C.sub.11 -C.sub.15 branched chain alkyl sulfates and the C.sub.12
-C.sub.14 linear chain alkyl sulfates.
Alkyl ethoxysulfate surfactants are preferably selected from the group
consisting of the C.sub.10 -C.sub.18 alkyl sulfates which have been
ethoxylated with from 0.5 to 20 moles of ethylene oxide per molecule. More
preferably, the alkyl ethoxysulfate surfactant is a C.sub.11 -C.sub.18
most preferably C.sub.11 -C.sub.15 alkyl sulfate which has been
ethoxylated with from 0.5 to 7, preferably from 1 to 5, moles of ethylene
oxide per molecule.
A particularly preferred aspect of the invention employs mixtures of the
preferred alkyl sulfate and alkyl ethoxysulfate surfactants. Such mixtures
have been disclosed in PCT Patent Application No. WO 93/18124.
Anionic Sulfonate Surfactants
Anionic sulfonate surfactants suitable for use herein include the salts of
C.sub.5 -C.sub.20 linear alkylbenzene sulfonates, alkyl ester sulfonates,
C.sub.6 -C.sub.22 primary or secondary alkane sulfonates, C.sub.6
-C.sub.24 olefin sulfonates, sulfonated polycarboxylic acids, alkyl
glycerol sulfonates, fatty acyl glycerol sulfonates, fatty oleyl glycerol
sulfonates, and any mixtures thereof.
Anionic Carboxylate Surfactant
Suitable anionic carboxylate surfactants include the alkyl ethoxy
carboxylates, the alkyl polyethoxy polycarboxylate surfactants and the
soaps (`alkyl carboxyls`), especially certain secondary soaps as described
herein.
Suitable alkyl ethoxy carboxylates include those with the formula
RO(CH.sub.2 CH.sub.2 O).sub.x CH.sub.2 COO.sup.31 M.sup.+ wherein R is a
C.sub.6 to C.sub.18 alkyl group, x ranges from 0 to 10, and the ethoxylate
distribution is such that, on a weight basis, the amount of material where
x is 0 is less than 20% and M is a cation. Suitable alkyl polyethoxy
polycarboxylate surfactants include those having the formula
RO--(CHR.sub.1 --CHR.sub.2 --O)--R.sub.3 wherein R is a C.sub.6 to
C.sub.18 alkyl group, x is from 1 to 25, R.sub.1 and R.sub.2 are selected
from the group consisting of hydrogen, methyl acid radical, succinic acid
radical, hydroxysuccinic acid radical, and mixtures thereof, and R.sub.3
is selected from the group consisting of hydrogen, substituted or
unsubstituted hydrocarbon having between 1 and 8 carbon atoms, and
mixtures thereof.
Suitable soap surfactants include the secondary soap surfactants which
contain a carboxyl unit connected to a secondary carbon. Preferred
secondary soap surfactants for use herein are water-soluble members
selected from the group consisting of the water-soluble salts of
2-methyl-1-undecanoic acid, 2-ethyl-1-decanoic acid, 2-propyl-1-nonanoic
acid, 2-butyl-1-octanoic acid and 2-pentyl-1-heptanoic acid. Certain soaps
may also be included as suds suppressors.
Alkali Metal Sarcosinate Surfactant
Other suitable anionic surfactants are the alkali metal sarcosinates of
formula R--CON (R.sup.1) CH.sub.2 COOM, wherein R is a C.sub.5 -C.sub.17
linear or branched alkyl or alkenyl group, R.sup.1 is a C.sub.1 -C.sub.4
alkyl group and M is an alkali metal ion. Preferred examples are the
myristyl and oleoyl methyl sarcosinates in the form of their sodium salts.
Oxygen-releasing Bleaching System
An optional component of the detergent composition is an oxygen-releasing
bleaching system. In one preferred aspect the bleaching system contains a
hydrogen peroxide source and an organic peroxyacid bleach precursor
compound. The production of the organic peroxyacid occurs by an in situ
reaction of the precursor with a source of hydrogen peroxide. Preferred
sources of hydrogen peroxide include inorganic perhydrate bleaches. In an
alternative preferred aspect a preformed organic peroxyacid is
incorporated directly into the composition. Compositions containing
mixtures of a hydrogen peroxide source and organic peroxyacid precursor in
combination with a preformed organic peroxyacid are also envisaged.
Inorganic Perhydrate Bleaches
The compositions in accord with the invention preferably include a hydrogen
peroxide source, as an oxygen-releasing bleach. Suitable hydrogen peroxide
sources include the inorganic perhydrate salts.
The inorganic perhydrate salts are normally incorporated in the form of the
sodium salt at a level of from 1% to 40% by weight, more preferably from
2% to 30% by weight and most preferably from 5% to 25% by weight of the
compositions.
Examples of inorganic perhydrate salts include perborate, percarbonate,
perphosphate, persulfate and persilicate salts. The inorganic perhydrate
salts are normally the alkali metal salts. The inorganic perhydrate salt
may be included as the crystalline solid without additional protection.
For certain perhydrate salts however, the preferred executions of such
granular compositions utilise a coated form of the material which provides
better storage stability for the perhydrate salt in the granular product.
Sodium perborate can be in the form of the monohydrate of nominal formula
NaBO.sub.2 H.sub.2 O.sub.2 or the tetrahydrate NaBO.sub.2 H.sub.2
O.sub.2.3H.sub.2 O.
Alkali metal percarbonates, particularly sodium percarbonate are preferred
perhydrates for inclusion in compositions in accordance with the
invention. Sodium percarbonate is an addition compound having a formula
corresponding to 2Na.sub.2 CO.sub.3.3H.sub.2 O.sub.2, and is available
commercially as a crystalline solid. Sodium percarbonate, being a hydrogen
peroxide addition compound tends on dissolution to release the hydrogen
peroxide quite rapidly which can increase the tendency for localised high
bleach concentrations to arise. The percarbonate is most preferably
incorporated into such compositions in a coated form which provides
in-product stability.
A suitable coating material providing in product stability comprises mixed
salt of a water soluble alkali metal sulphate and carbonate. Such coatings
together with coating processes have previously been described in
GB-1,466,799, granted to Interox on Mar. 9, 1977. The weight ratio of the
mixed salt coating material to percarbonate lies in the range from 1:200
to 1:4, more preferably from 1:99 to 1:9, and most preferably from 1:49 to
1:19. Preferably, the mixed salt is of sodium sulphate and sodium
carbonate which has the general formula Na.sub.2 SO.sub.4.n.Na.sub.2
CO.sub.3 wherein n is from 0. 1 to 3, preferably n is from 0.3 to 1.0 and
most preferably n is from 0.2 to 0.5.
Other coatings which contain silicate (alone or with borate salts or boric
acids or other inorganics), waxes, oils, fatty soaps can also be used
advantageously within the present invention.
Potassium peroxymonopersulfate is another inorganic perhydrate salt of
utility in the compositions herein.
Peroxyacid Bleach Precursor
Peroxyacid bleach precursors are compounds which react with hydrogen
peroxide in a perhydrolysis reaction to produce a peroxyacid. Generally
peroxyacid bleach precursors may be represented as
##STR3##
where L is a leaving group and X is essentially any functionality, such
that on perhydrolysis the structure of the peroxyacid produced is
##STR4##
Peroxyacid bleach precursor compounds are preferably incorporated at a
level of from 0.5% to 20% by weight, more preferably from 1% to 10% by
weight, most preferably from 1.5% to 5% by weight of the compositions.
Suitable peroxyacid bleach precursor compounds typically contain one or
more N- or O-acyl groups, which precursors can be selected from a wide
range of classes. Suitable classes include anhydrides, esters, imides,
lactams and acylated derivatives of imidazoles and oximes. Examples of
useful materials within these classes are disclosed in GB-A-1586789.
Suitable esters are disclosed in GB-A-836988, 864798, 1147871, 2143231 and
EP-A-0170386.
Leaving Groups
The leaving group, hereinafter L group, must be sufficiently reactive for
the perhydrolysis reaction to occur within the optimum time frame (e.g., a
wash cycle). However, if L is too reactive, this activator will be
difficult to stabilise for use in a bleaching composition.
Preferred L groups are selected from the group consisting of:
##STR5##
and mixtures thereof, wherein R.sup.1 is an alkyl, aryl, or alkaryl group
containing from 1 to 14 carbon atoms, R.sup.3 is an alkyl chain containing
from 1 to 8 carbon atoms, R.sup.4 is H or R.sup.3, and Y is H or a
solubilizing group. Any of R.sup.1, R.sup.3 and R.sup.4 may be substituted
by essentially any functional group including, for example alkyl, hydroxy,
alkoxy, halogen, amine, nitrosyl, amide and ammonium or alkyl ammonium
groups.
The preferred solubilizing groups are --SO.sub.3.sup.- M.sup.+,
-CO.sub.2.sup.- M.sup.+, --SO.sub.4.sup.- M.sup.+, --N.sup.+
(R.sup.3).sub.4 X.sup.- and O<----N(R.sup.3).sub.3 and most preferably
--SO.sub.3.sup.- M.sup.+ and --CO.sub.2.sup.- M.sup.+ wherein R.sup.3 is
an alkyl chain containing from 1 to 4 carbon atoms, M is a cation which
provides solubility to the bleach activator and X is an anion which
provides solubility to the bleach activator. Preferably, M is an alkali
metal, ammonium or substituted ammonium cation, with sodium and potassium
being most preferred, and X is a halide, hydroxide, methylsulfate or
acetate anion.
Perbenzoic Acid Precursor
Perbenzoic acid precursor compounds provide perbenzoic acid on
perhydrolysis.
Suitable O-acylated perbenzoic acid precursor compounds include the
substituted and unsubstituted benzoyl oxybenzene sulfonates, including for
example benzoyl oxybenzene sulfonate:
##STR6##
Also suitable are the benzoylation products of sorbitol, glucose, and all
saccharides with benzoylating agents, including for example:
##STR7##
Perbenzoic acid precursor compounds of the imide type include N-benzoyl
succinimide, tetrabenzoyl ethylene diamine and the N-benzoyl substituted
ureas. Suitable imidazole type perbenzoic acid precursors include
N-benzoyl imidazole and N-benzoyl benzimidazole and other useful N-acyl
group-containing perbenzoic acid precursors include N-benzoyl pyrrolidone,
dibenzoyl taurine and benzoyl pyroglutamic acid.
Other perbenzoic acid precursors include the benzoyl diacyl peroxides, the
benzoyl tetraacyl peroxides, and the compound having the formula:
##STR8##
Phthalic anhydride is another suitable perbenzoic acid precursor compound
herein:
##STR9##
Suitable N-acylated lactam perbenzoic acid precursors have the formula:
##STR10##
wherein n is from 0 to 8, preferably from 0 to 2, and R.sup.6 is a benzoyl
group.
Perbenzoic Acid Derivative Precursors
Perbenzoic acid derivative precursors provide substituted perbenzoic acids
on perhydrolysis.
Suitable substituted perbenzoic acid derivative precursors include any of
the herein disclosed perbenzoic precursors in which the benzoyl group is
substituted by essentially any non-positively charged (i.e.; non-cationic)
functional group including, for example alkyl, hydroxy, alkoxy, halogen,
amine, nitrosyl and amide groups.
A preferred class of substituted perbenzoic acid precursor compounds are
the amide substituted compounds of the following general formulae:
##STR11##
wherein R.sup.1 is an aryl or alkaryl group with from 1 to 14 carbon
atoms, R.sup.2 is an arylene, or alkarylene group containing from 1 to 14
carbon atoms, and R.sup.5 is H or an alkyl, aryl, or alkaryl group
containing 1 to 10 carbon atoms and L can be essentially any leaving
group. R.sup.1 preferably contains from 6 to 12 carbon atoms. R.sup.2
preferably contains from 4 to 8 carbon atoms. R.sup.1 may be aryl,
substituted aryl or alkylaryl containing branching, substitution, or both
and may be sourced from either synthetic sources or natural sources
including for example, tallow fat. Analogous structural variations are
permissible for R.sup.2. The substitution can include alkyl, aryl,
halogen, nitrogen, sulphur and other typical substituent groups or organic
compounds. R.sup.5 is preferably H or methyl. R.sup.1 and R.sup.5 should
not contain more than 18 carbon atoms in total. Amide substituted bleach
activator compounds of this type are described in EP-A-0170386.
Cationic Peroxyacid Precursors
Cationic peroxyacid precursor compounds produce cationic peroxyacids on
perhydrolysis.
Typically, cationic peroxyacid precursors are formed by substituting the
peroxyacid part of a suitable peroxyacid precursor compound with a
positively charged functional group, such as an ammonium or alkyl ammonium
group, preferably an ethyl or methyl ammonium group.
Cationic peroxyacid precursors are typically present in the compositions as
a salt with a suitable anion, such as for example a halide ion or a
methylsulfate ion.
The peroxyacid precursor compound to be so cationically substituted may be
a perbenzoic acid, or substituted derivative thereof, precursor compound
as described hereinbefore. Alternatively, the peroxyacid precursor
compound may be an alkyl percarboxylic acid precursor compound or an amide
substituted alkyl peroxyacid precursor as described hereinafter
Cationic peroxyacid precursors are described in U.S. Pat. Nos. 4,904,406;
4,751,015; 4,988,451; 4,397,757; 5,269,962; 5,127,852; 5,093,022;
5,106,528; U.K. 1,382,594; EP 475,512, 458,396 and 284,292; and in JP
87-318,332.
Suitable cationic peroxyacid precursors include any of the ammonium or
alkyl ammonium substituted alkyl or benzoyl oxybenzene sulfonates,
N-acylated caprolactams, and monobenzoyltetraacetyl glucose benzoyl
peroxides.
A preferred cationically substituted benzoyl oxybenzene sulfonate is the
4-(trimethyl ammonium) methyl derivative of benzoyl oxybenzene sulfonate:
##STR12##
A preferred cationically substituted alkyl oxybenzene sulfonate has the
formula:
##STR13##
Preferred cationic peroxyacid precursors of the N-acylated caprolactam
class include the trialkyl ammonium methylene benzoyl caprolactams,
particularly trimethyl ammonium methylene benzoyl caprolactam:
##STR14##
Other preferred cationic peroxyacid precursors of the N-acylated
caprolactam class include the trialkyl ammonium methylene alkyl
caprolactams:
##STR15##
where n is from 0 to 12, particularly from 1 to 5.
Another preferred cationic peroxyacid precursor is 2-(N,N,N-trimethyl
ammonium) ethyl sodium 4-sulphophenyl carbonate chloride.
Alkyl Percarboxylic Acid Bleach Precursors
Alkyl percarboxylic acid bleach precursors form percarboxylic acids on
perhydrolysis. Preferred precursors of this type provide peracetic acid on
perhydrolysis.
Preferred alkyl percarboxylic precursor compounds of the imide type include
the N-,N,N.sup.1 N.sup.1 tetra acetylated alkylene diamines wherein the
alkylene group contains from 1 to 6 carbon atoms, particularly those
compounds in which the alkylene group contains 1, 2 and 6 carbon atoms.
Tetraacetyl ethylene diamine (TAED) is particularly preferred.
Other preferred alkyl percarboxylic acid precursors include sodium
3,5,5-tri-methyl hexanoyloxybenzene sulfonate (iso-NOBS), sodium
nonanoyloxybenzene sulfonate (NOBS), sodium acetoxybenzene sulfonate (ABS)
and penta acetyl glucose.
Amide Substituted Alkyl Peroxyacid Precursors
Amide substituted alkyl peroxyacid precursor compounds are also suitable,
including those of the following general formulae:
##STR16##
wherein R.sup.1 is an aLkyl group with from 1 to 14 carbon atoms, R.sup.2
is an alkylene group containing from 1 to 14 carbon atoms, and R.sup.5 is
H or an alkyl group containing 1 to 10 carbon atoms and L can be
essentially any leaving group. R.sup.1 preferably contains from 6 to 12
carbon atoms. R.sup.2 preferably contains from 4 to 8 carbon atoms.
R.sup.1 may be straight chain or branched alkyl containing branching,
substitution, or both and may be sourced from either synthetic sources or
natural sources including for example, tallow fat. Analogous structural
variations are permissible for R.sup.2. The substitution can include
alkyl, halogen, nitrogen, sulphur and other typical substituent groups or
organic compounds. R.sup.5 is preferably H or methyl. R.sup.1 and R.sup.5
should not contain more than 18 carbon atoms in total. Amide substituted
bleach activator compounds of this type are described in EP-A-0170386.
Benzoxazin Organic Peroxyacid Precursors
Also suitable are precursor compounds of the benzoxazin-type, as disclosed
for example in EP-A-332,294 and EP-A-482,807, particularly those having
the formula:
##STR17##
including the substituted benzoxazins of the type
##STR18##
wherein R.sub.1 is H, alkyl, alkaryl, aryl, arylalkyl, and wherein
R.sub.2, R.sub.3, R.sub.4, and R.sub.5 may be the same or different
substituents selected from H, halogen, alkyl, alkenyl, aryl, hydroxyl,
alkoxyl, amino, alkyl amino, COOR.sub.6 (wherein R.sub.6 is H or an alkyl
group) and carbonyl functions.
An especially preferred precursor of the benzoxazin-type is:
##STR19##
Preformed Organic Peroxyacid
The organic peroxyacid bleaching system may contain, in addition to, or as
an alternative to, an organic peroxyacid bleach precursor compound, a
preformed organic peroxyacid, typically at a level of from 0.5% to 25% by
weight, more preferably from 1% to 10% by weight of the composition.
A preferred class of organic peroxyacid compounds are the amide substituted
compounds of the following general formulae:
##STR20##
wherein R.sup.1 is an alkyl, aryl or alkaryl group with from 1 to 14
carbon atoms, R.sup.2 is an alkylene, arylene, and alkarylene group
containing from 1 to 14 carbon atoms, and R.sup.5 is H or an alkyl, aryl,
or alkaryl group containing 1 to 10 carbon atoms. R.sup.1 preferably
contains from 6 to 12 carbon atoms. R.sup.2 preferably contains from 4 to
8 carbon atoms. R.sup.1 may be straight chain or branched alkyl,
substituted aryl or alkylaryl containing branching, substitution, or both
and may be sourced from either synthetic sources or natural sources
including for example, tallow fat. Analogous structural variations are
permissible for R.sup.2. The substitution can include alkyl, aryl,
halogen, nitrogen, sulphur and other typical substituent groups or organic
compounds. R.sup.5 is preferably H or methyl. R.sup.1 and R.sup.5 should
not contain more than 18 carbon atoms in total. Amide substituted organic
peroxyacid compounds of this type are described in EP-A-0170386.
Other organic peroxyacids include diacyl and tetraacylperoxides, especially
diperoxydodecanedioc acid, diperoxytetradecanedioc acid, and
diperoxyhexadecanedioc acid. Dibenzoyl peroxide is a preferred organic
peroxyacid herein. Mono- and diperazelaic acid, mono- and diperbrassylic
acid, and N-phthaloylaminoperoxicaproic acid are also suitable herein.
Water-soluble Builder Compound
The compositions of the present invention may contain as a highly preferred
component a water-soluble builder compound, typically present at a level
of from 1% to 80% by weight, preferably from 10% to 70% by weight, most
preferably from 20% to 60% by weight of the composition. Suitable
water-soluble builder compounds include the water soluble monomeric
polycarboxylates, or their acid forms, homo or copolymeric polycarboxylic
acids or their salts in which the polycarboxylic acid comprises at least
two carboxylic radicals separated from each other by not more than two
carbon atoms, carbonates, bicarbonates, borates, phosphates, and mixtures
thereof.
The carboxylate or polycarboxylate builder can be monomeric or oligomeric
in type although monomeric polycarboxylates are generally preferred for
reasons of cost and performance.
Suitable carboxylates containing one carboxy group include the water
soluble salts of lactic acid, glycolic acid and ether derivatives thereof.
Polycarboxylates containing two carboxy groups include the water-soluble
salts of succinic acid, malonic acid, (ethylenedioxy) diacetic acid,
maleic acid, diglycolic acid, tartaric acid, tartronic acid and fumaric
acid, as well as the ether carboxylates and the sulfmyl carboxylates.
Polycarboxylates containing three carboxy groups include, in particular,
water-soluble citrates, aconitrates and citraconates as well as succinate
derivatives such as the carboxymethyloxysuccinates described in British
Patent No. 1,379,241, lactoxysuccinates described in British Patent No.
1,389,732, and aminosuccinates described in Netherlands Application
7205873, and the oxypolycarboxylate materials such as 2-oxa-1,1,3-propane
tricarboxylates described in British Patent No. 1,387,447.
Polycarboxylates containing four carboxy groups include oxydisuccinates
disclosed in British Patent No. 1,261,829, 1,1,2,2-ethane
tetracarboxylates, 1,1,3,3-propane tetracarboxylates and 1,1,2,3-propane
tetracarboxylates. Polycarboxylates containing sulfo substituents include
the sulfosuccinate derivatives disclosed in British Patent Nos. 1,398,421
and 1,398,422 and in U.S. Pat. No. 3,936,448, and the sulfonated pyrolysed
citrates described in British Patent No. 1,439,000.
Alicyclic and heterocyclic polycarboxylates include
cyclopentane-cis,cis,cis-tetracarboxylates, cyclopentadienide
pentacarboxylates, 2,3,4,5-tetrahydrofuran-cis,cis,cis-tetracarboxylates,
2,5-tetrahydrofuran-cis-dicarboxylates,
2,2,5,5-tetrahydrofuran-tetracarboxylates,
1,2,3,4,5,6-hexane-hexacarboxylates and carboxymethyl derivatives of
polyhydric alcohols such as sorbitol, mannitol and xylitol. Aromatic
polycarboxylates include mellitic acid, pyromellitic acid and the phthalic
acid derivatives disclosed in British Patent No. 1,425,343.
Of the above, the preferred polycarboxylates are hydroxycarboxylates
containing up to three carboxy groups per molecule, more particularly
citrates.
The parent acids of the monomeric or oligomeric polycarboxylate chelating
agents or mixtures thereof with their salts, e.g. citric acid or
citrate/citric acid mixtures are also contemplated as useful builder
components.
Borate builders, as well as builders containing borate-forming materials
that can produce borate under detergent storage or wash conditions can
also be used but are not preferred at wash conditions less that about
50.degree. C., especially less than about 40.degree. C.
Examples of carbonate builders are the alkaline earth and alkali metal
carbonates, including sodium carbonate and sesqui-carbonate and mixtures
thereof with ultra-fine calcium carbonate as disclosed in German Patent
Application No. 2,321,001 published on Nov. 15, 1973.
Specific examples of water-soluble phosphate builders are the alkali metal
tripolyphosphates, sodium, potassium and ammonium pyrophosphate, sodium
and potassium and ammonium pyrophosphate, sodium and potassium
orthophosphate, sodium polymeta/phosphate in which the degree of
polymerization ranges from about 6 to 21, and salts of phytic acid.
Partially Soluble or Insoluble Builder Compound
The detergent compositions of the present invention may contain a partially
soluble or insoluble builder compound, typically present at a level of
from 1% to 80% by weight, preferably from 10% to 70% by weight, most
preferably from 20% to 60% weight of the composition.
Examples of largely water insoluble builders include the sodium
aluminosilicates.
Suitable aluminosilicate zeolites have the unit cell formula Na.sub.z
[(AlO.sub.2).sub.z (SiO.sub.2)y]. xH.sub.2 O wherein z and y are at least
6; the molar ratio of z to y is from 1.0 to 0.5 and x is at least 5,
preferably from 7.5 to 276, more preferably from 10 to 264. The
aluminosilicate material are in hydrated form and are preferably
crystalline, containing from 10% to 28%, more preferably from 18% to 22%
water in bound form.
The aluminosilicate zeolites can be naturally occurring materials, but are
preferably synthetically derived. Synthetic crystalline aluminosilicate
ion exchange materials are available under the designations Zeolite A,
Zeolite B, Zeolite P, Zeolite X, Zeolite HS and mixtures thereof. Zeolite
A has the formula
Na.sub.12 [AlO.sub.2).sub.12 (SiO.sub.2).sub.12 ].xH.sub.2 O
wherein x is from 20 to 30, especially 27. Zeolite X has the formula
Na.sub.86 [(AlO.sub.2).sub.86 (SiO.sub.2).sub.106 ].276H.sub.2 O. Zeolite
MAP, as disclosed in P-B-384,070 is a preferred zeolite builder herein.
Water-soluble Bismuth Compound
The compositions used in this invention may contain a water-soluble bismuth
compound, preferably present at a level of from 0.005% to 20%, more
preferably from 0.01% to 5%, most preferably from 0.1% to 1% by weight of
the compositions.
The water-soluble bismuth compound may be essentially any salt or complex
of bismuth with essentially any inorganic or organic counter anion.
Preferred inorganic bismuth salts are selected from the bismuth
trihalides, bismuth nitrate and bismuth phosphate. Bismuth acetate and
citrate are preferred salts with an organic counter anion.
Water-soluble Sulfate Salt
The compositions may optionally contain a water-soluble sulfate salt,
preferably present at a level of from 0.1% to 40%, more preferably from 1%
to 30%, most preferably from 5% to 25% by weight of the compositions.
The water-soluble sulfate salt may be essentially any salt of sulfate with
any counter cation. Preferred salts are selected from the sulfates of the
alkali and alkaline earth metals, particularly sodium sulfate.
Corrosion Inhibitor Compound
The compositions may contain corrosion inhibitors preferably selected from
organic silver coating agents, particularly paraffin, nitrogen-containing
corrosion inhibitor compounds and Mn(II) compounds, particularly Mn(II)
salts of organic ligands.
Organic Silver Coating Agents
Organic silver coating agent may be incorporated in automatic dishwashing
compositions herein at a level of from 0.05% to 10%, preferably from 0.1%
to 5% by weight of the total composition.
The functional role of the silver coating agent is to form `in use` a
protective coating layer on any silverware components of the washload to
which the compositions of the invention are being applied. The silver
coating agent should hence have a high affinity for attachment to solid
silver surfaces, particularly when present in as a component of an aqueous
washing and bleaching solution with which the solid silver surfaces are
being treated.
Suitable organic silver coating agents herein include fatty esters of mono-
or polyhydric alcohols having from 1 to about 40 carbon atoms in the
hydrocarbon chain.
The fatty acid portion of the fatty ester can be obtained from mono- or
poly-carboxylic acids having from 1 to about 40 carbon atoms in the
hydrocarbon chain. Suitable examples of monocarboxylic fatty acids include
behenic acid, stearic acid, oleic acid, palmitic acid, myristic acid,
lauric acid, acetic acid, propionic acid, butyric acid, isobutyric acid,
Valerie acid, lactic acid, glycolic acid and
.beta.,.beta.'-dihydroxyisobutyric acid. Examples of suitable
polycarboxylic acids include: n-butyl-malonic acid, isocitric acid, citric
acid, maleic acid, malic acid and succinic acid.
The fatty alcohol radical in the fatty ester can be represented by mono- or
polyhydric alcohols having from 1 to 40 carbon atoms in the hydrocarbon
chain. Examples of suitable fatty alcohols include; behenyl, arachidyl,
cocoyl, oleyl and lauryl alcohol, ethylene glycol, glycerol, ethanol,
isopropanol, vinyl alcohol, diglycerol, xylitol, sucrose, erythritol,
pentaerythritol, sorbitol or sorbitan.
Preferably, the fatty acid and/or fatty alcohol group of the fatty ester
adjunct material have from 1 to 24 carbon atoms in the alkyl chain.
Preferred fatty esters herein are ethylene glycol, glycerol and sorbitan
esters wherein the fatty acid portion of the ester normally comprises a
species selected from behenic acid, stearic acid, oleic acid, palmitic
acid or myristic acid.
The glycerol esters are also highly preferred. These are the mono-, di- or
tri-esters of glycerol and the fatty acids as defined above.
Specific examples of fatty alcohol esters for use herein include: stearyl
acetate, palmityl di-lactate, cocoyl isobutyrate, oleyl maleate, oleyl
dimaleate, and tallowyl proprionate. Fatty acid esters useful herein
include: xylitol monopalmitate, pentaerythritol monostearate, sucrose
monostearate, glycerol monostearate, ethylene glycol monostearate,
sorbitan esters. Suitable sorbitan esters include sorbitan monostearate,
sorbitan palmitate, sorbitan monolaurate, sorbitan monomyristate, sorbitan
monobehenate, sorbitan mono-oleate, sorbitan dilaurate, sorbitan
distearate, sorbitan dibehenate, sorbitan dioleate, and also mixed
tallowalkyl sorbitan mono- and di-esters.
Glycerol monostearate, glycerol mono-oleate, glycerol monopalmitate,
glycerol monobehenate, and glycerol distearate are preferred glycerol
esters herein.
Suitable organic silver coating agents include triglycerides, mono or
diglycerides, and wholly or partially hydrogenated derivatives thereof,
and any mixtures thereof. Suitable sources of fatty acid esters include
vegetable and fish oils and animal fats. Suitable vegetable oils include
soy bean oil, cotton seed oil, castor oil, olive oil, peanut oil,
safflower oil, sunflower oil, rapeseed oil, grapeseed oil, palm oil and
corn oil.
Waxes, including microcrystalline waxes are suitable organic silver coating
agents herein. Preferred waxes have a melting point in the range from
about 35.degree. C. to about 110.degree. C. and comprise generally from 12
to 70 carbon atoms. Preferred are petroleum waxes of the paraffin and
microcrystalline type which are composed of long-chain saturated
hydrocarbon compounds.
Alginates and gelatin are suitable organic silver coating agents herein.
Dialkyl amine oxides such as C.sub.12 -C.sub.20 methylamine oxide, and
dialkyl quaternary ammonium compounds and salts, such as the C.sub.12
-C.sub.20 methylammonium halides are also suitable.
Other suitable organic silver coating agents include certain polymeric
materials. Polyvinylpyrrolidones with an average molecular weight of from
12,000 to 700,000, polyethylene glycols (PEG) with an average molecular
weight of from 600 to 10,000, polyamine N-oxide polymers, copolymers of
N-vinylpyrrolidone and N-vinylimidazole, and cellulose derivatives such as
methylcellulose, carboxymethylcellulose and hydroxyethylcellulose are
examples of such polymeric materials.
Certain perfume materials, particularly those demonstrating a high
substantivity for metallic surfaces, are also useful as the organic silver
coating agents herein.
Soil Release Agent
Polymeric soil release agents can also be used as an organic silver coating
agent. Such soil release agents are also preferred ingredients of laundry
detergent compositions herein, for their soil release capability.
Suitable polymeric soil release agents include those soil release agents
having: (a) one or more nonionic hydrophile components consisting
essentially of (i) polyoxyethylene segments with a degree of
polymerization of at least 2, or (ii) oxypropylene or polyoxypropylene
segments with a degree of polymerization of from 2 to 10, wherein said
hydrophile segment does not encompass any oxypropylene unit unless it is
bonded to adjacent moieties at each end by ether linkages, or (iii) a
mixture of oxyalkylene units comprising oxyethylene and from 1 to about 30
oxypropylene units, said hydrophile segments preferably comprising at
least about 25% oxyethylene units and more preferably, especially for such
components having about 20 to 30 oxypropylene units, at least about 50%
oxyethylene units; or (b) one or more hydrophobe components comprising (i)
C.sub.3 oxyalkylene terephthalate segments, wherein, if said hydrophobe
components also comprise oxyethylene terephthalate, the ratio of
oxyethylene terephthalate:C3 oxyalkylene terephthalate units is about 2:1
or lower, (ii) C.sub.4 -C.sub.6 alkylene or oxy C.sub.4 -C.sub.6 alkylene
segments, or mixtures therein, (iii) poly (vinyl ester) segments,
preferably polyvinyl acetate, having a degree of polymerization of at
least 2, or (iv) C.sub.1 -C.sub.4 alkyl ether or C.sub.4 hydroxyalkyl
ether substituents, or mixtures therein, wherein said substituents are
present in the form of C.sub.1 -C.sub.4 alkyl ether or C.sub.4
hydroxyalkyl ether cellulose derivatives, or mixtures therein, or a
combination of (a) and (b).
Typically, the polyoxyethylene segments of (a)(i) will have a degree of
polymerization of from about 200, although higher levels can be used,
preferably from 3 to about 150, more preferably from 6 to about 100.
Suitable oxy C.sub.4 -C.sub.6 alkylene hydrophobe segments include, but
are not limited to, end-caps of polymeric soil release agents such as
MO.sub.3 S(CH.sub.2).sub.n OCH.sub.2 CH.sub.2 O--, where M is sodium and n
is an integer from 4-6, as disclosed in U.S. Pat. No. 4,721,580, issued
Jan. 26, 1988 to Gosselink.
Polymeric soil release agents useful herein also include cellulosic
derivatives such as hydroxyether cellulosic polymers, copolymeric blocks
of ethylene terephthalate or propylene terephthalate with polyethylene
oxide or polypropylene oxide terephthalate, and the like. Such agents are
commercially available and include hydroxyethers of cellulose such as
METHOCEL (Dow). Cellulosic soil release agents for use herein also include
those selected from the group consisting of C.sub.1 -C.sub.4 alkyl and
C.sub.4 hydroxyalkyl cellulose; see U.S. Pat. No. 4,000,093, issued Dec.
28, 1976 to Nicol, et al.
Soil release agents characterised by poly(vinyl ester) hydrophobe segments
include graft copolymers of poly(vinyl ester), e.g., C.sub.1 -C.sub.6
vinyl esters, preferably poly(vinyl acetate) grafted onto polyalkylene
oxide backbones, such as polyethylene oxide backbones. See European Patent
Application 0 219 048, published Apr. 22, 1987 by Kud, et al.
Another suitable soil release agent is a copolymer having random blocks of
ethylene terephthalate and polyethylene oxide (PEO) terephthalate. The
molecular weight of this polymeric soil release agent is in the range of
from about 25,000 to about 55,000. See U.S. Pat. No. 3,959,230 to Hays,
issued May 25, 1976 and U.S. Pat. No. 3,893,929 to Basadur issued Jul. 8,
1975.
Another suitable polymeric soil release agent is a polyester with repeat
units of ethylene terephthalate units contains 10-15% by weight of
ethylene terephthalate units together with 90-80% by weight of
polyoxyethylene terephthalate units, derived from a polyoxyethylene glycol
of average molecular weight 300-5,000.
Another suitable polymeric soil release agent is a sulfonated product of a
substantially linear ester oligomer comprised of an oligomeric ester
backbone of terephthaloyl and oxyalkyleneoxy repeat units and terminal
moieties covalently attached to the backbone. These soil release agents
are described fully in U.S. Pat. No. 4,968,451, issued Nov. 6, 1990 to J.
J. Scheibel and E. P. Gosselink. Other suitable polymeric soil release
agents include the terephthalate polyesters of U.S. Pat. No. 4,711,730,
issued Dec. 8, 1987 to Gosselink et al, the anionic end-capped oligomeric
esters of U.S. Pat. No. 4,721,580, issued Jan. 26, 1988 to Gosselink, and
the block polyester oligomeric compounds of U.S. Pat. No. 4,702,857,
issued Oct. 27, 1987 to Gosselink. Other polymeric soil release agents
also include the soil release agents of U.S. Pat. No. 4,877,896, issued
Oct. 31, 1989 to Maldonado et al, which discloses anionic, especially
sulfoarolyl, end-capped terephthalate esters.
Another soil release agent is an oligomer with repeat units of
terephthaloyl units, sulfoisoterephthaloyl units, oxyethyleneoxy and
oxy-1,2-propylene units. The repeat units form the backbone of the
oligomer and are preferably terminated with modified isethionate end-caps.
A particularly preferred soil release agent of this type comprises about
one sulfoisophthaloyl unit, 5 terephthaloyl units, oxyethyleneoxy and
oxy-1,2-propyleneoxy units in a ratio of from about 1.7 to about 1.8, and
two end-cap units of sodium 2-(2-hydroxyethoxy)-ethanesulfonate.
A preferred organic silver coating agent is a paraffin oil, typically a
predominantly branched aliphatic hydrocarbon having a number of carbon
atoms in the range of from 20 to 50; preferred paraffin oil selected from
predominantly branched C.sub.25-45 species with a ratio of cyclic to
noncyclic hydrocarbons of from 1:10 to 2:1, preferably from 1:5 to 1:1. A
paraffin oil meeting these characteristics, having a ratio of cyclic to
noncyclic hydrocarbons of about 32:68, is sold by Wintershall, Salzbergen,
Germany, under the trade name WINOG 70.
Nitrogen-Containing Corrosion Inhibitor Compounds
Suitable nitrogen-containing corrosion inhibitor compounds include
imidazole and derivatives thereof such as benzimidazole, 2-heptadecyl
imidazole and those imidazole derivatives described in Czech Patent No.
139, 279 and British Patent GB-A-1,137,741, which also discloses a method
for making imidazole compounds.
Also suitable as nitrogen-containing corrosion inhibitor compounds are
pyrazole compounds and their derivatives, particularly those where the
pyrazole is substituted in any of the 1, 3, 4 or 5 positions by
substituents R.sub.1, R.sub.3, R.sub.4 and R.sub.5 where R.sub.1 is any of
H, CH.sub.2 OH, CONH.sub.3, or COCH.sub.3, R.sub.3 and R.sub.5 are any of
C.sub.1 -C.sub.20 alkyl or hydroxyl, and R.sub.4 is any of H, NH.sub.2 or
NO.sub.2.
Other suitable nitrogen-containing corrosion inhibitor compounds include
benzotriazole, 2-mercaptobenzothiazole,
1-phenyl-5-mercapto-1,2,3,4-tetrazole, thionalide, morpholine, melamine,
distearylamine, stearoyl stearamide, cyanuric acid, aminotriazole,
aminotetrazole and indazole.
Nitrogen-containing compounds such as amines, especially distearylamine and
ammonium compounds such as ammonium chloride, ammonium bromide, ammonium
sulphate or diammonium hydrogen citrate are also suitable.
Mn(II) Corrosion Inhibitor Compounds
The compositions may contain an Mn(II) corrosion inhibitor compound. The
Mn(II) compound is preferably incorporated at a level of from 0.005% to 5%
by weight, more preferably from 0.01% to 1%, most preferably from 0.02% to
0.4% by weight of the compositions. Preferably, the Mn(II) compound is
incorporated at a level to provide from 0.1 ppm to 250 ppm, more
preferably from 0.5 ppm to 50 ppm, most preferably from 1 ppm to 20 ppm by
weight of Mn(II) ions in any bleaching solution.
The Mn (II) compound may be an inorganic salt in anhydrous, or any hydrated
forms. Suitable salts include manganese sulphate, manganese carbonate,
manganese phosphate, manganese nitrate, manganese acetate and manganese
chloride. The Mn(II) compound may be a salt or complex of an organic fatty
acid such as manganese acetate or manganese stearate.
The Mn(II) compound may be a salt or complex of an organic ligand. In one
preferred aspect the organic ligand is a heavy metal ion sequestrant. In
another preferred aspect the organic ligand is a crystal growth inhibitor.
Other Corrosion Inhibitor Compounds
Other suitable additional corrosion inhibitor compounds include, mercaptans
and diols, especially mercaptans with 4 to 20 carbon atoms including
lauryl mercaptan, thiophenol, thionapthol, thionalide and thioanthranol.
Also suitable are saturated or unsaturated C.sub.10 -C.sub.20 fatty acids,
or their salts, especially aluminium tristearate. The C.sub.12 -C.sub.20
hydroxy fatty acids, or their salts, are also suitable. Phosphonated
octa-decane and other anti-oxidants such as betahydroxytoluene (BHT) are
also suitable.
Copolymers of butadiene and maleic acid, particularly those supplied under
the trade reference no. 07787 by Polysciences Inc have been found to be of
particular utility as corrosion inhibitor compounds.
Total Available Oxygen (AvO) Level
It has been found that, for the optimal anti-silver tarnishing of automatic
dishwashing compositions performance herein, the level of available oxygen
in the present compositions, measured in units of % available oxygen by
weight of the composition, is preferably controlled; the level of
available oxygen should hence preferably be in the range from 0.3% to
2.5%, preferably from 0.5% to 1.7%, more preferably from 0.6% to 1.5%,
most preferably from 0.7% to 1.2%, measured according to the method
described hereunder.
Rate of Release of AvO
The rate of release of available oxygen is preferably also controlled; the
rate of release of available oxygen from the compositions herein
preferably should be such that, when using the method described
hereinafter, the available oxygen is not completely released from the
composition until after 3.5 minutes, preferably the available oxygen is
released in a time interval of from 3.5 minutes to 10.0 minutes, more
preferably from 4.0 minutes to 9.0 minutes, most preferably from 5.0
minutes to 8.5 minutes.
Method for Measuring Level of Total Available Oxygen (AvO) and Rate of
Release of AvO in a Detergent Composition
Method
1. A beaker of water (typically 2L) is placed on a stirrer Hotplate, and
the stirrer speed is selected to ensure that the product is evenly
dispersed through the solution.
2. The detergent composition (typically 8 g of product which has been
sampled down from a bulk supply using a Pascal sampler), is added and
simultaneously a stop clock is started.
3. The temperature control should be adjusted so as to maintain a constant
temperature of 20.degree. C. throughout the experiment.
4. Samples are taken from the detergent solution at 2 minute time intervals
for 20 minutes, starting after 1 minute, and are titrated by the
"titration procedure" described below to determine the level of available
oxygen at each point.
Titration Procedure
1. An aliquot from the detergent solution (above) and 2 ml sulphuric acid
are added into a stirred beaker
2. Approximately 0.2 g ammonium molybdate catalyst (tetra hydrate form) are
added
3. 3 mls of 10% sodium iodide solution are added
4. Titration with sodium thiosulphate is conducted until the end point. The
end point can be seen using either of two procedures. First procedure
consists simply in seeing the yellow iodine colour fading to clear. The
second and preferred procedure consists of adding soluble starch when the
yellow colour is becoming faint, turning the solution blue. More
thiosulphate is added until the end point is reached (blue starch complex
is decolourised).
The level of AvO, measured in units of % available oxygen by weight, for
the sample at each time interval corresponds to the amount of titre
according to the following equation
##EQU1##
AvO level is plotted versus time to determine the maximum level of AvO, and
the rate of release of AvO
Controlled Rate of Release--Means
A means may be provided for controlling the rate of release of oxygen
bleach to the wash solution.
Means for controlling the rate of release of the bleach may provide for
controlled release of peroxide species to the wash solution. Such means
could, for example, include controlling the release of any inorganic
perhydrate salt, acting as a hydrogen peroxide source, to the wash
solution.
Suitable controlled release means can include coating any suitable
component with a coating designed to provide the controlled release. The
coating may therefore, for example, comprise a poorly water soluble
material, or be a coating of sufficient thickness that the kinetics of
dissolution of the thick coating provide the controlled rate of release.
The coating material may be applied using various methods. Any coating
material is typically present at a weight ratio of coating material to
bleach of from 1:99 to 1:2, preferably from 1:49 to 1:9.
Suitable coating materials include triglycerides (e.g. partially)
hydrogenated vegetable oil, soy bean oil, cotton seed oil) mono or
diglycerides, microcrystalline waxes, gelatin, cellulose, fatty acids and
any mixtures thereof.
Other suitable coating materials can comprise the alkali and alkaline earth
metal sulphates, silicates and carbonates, including calcium carbonate and
silicas.
A preferred coating material, particularly for an inorganic perhydrate salt
bleach source, comprises sodium silicate of SiO.sub.2 :Na.sub.2 O ratio
from 1.8:1 to 3.0:1, preferably 1.8:1 to 2.4:1, and/or sodium
metasilicate, preferably applied at a level of from 2% to 10%, (normally
from 3% to 5%) of SiO.sub.2 by weight of the inorganic perhydrate salt.
Magnesium silicate can also be included in the coating.
Any inorganic salt coating materials may be combined with organic binder
materials to provide composite inorganic salt/organic binder coatings.
Suitable binders include the C.sub.10 -C.sub.20 alcohol ethoxylates
containing from 5-100 moles of ethylene oxide per mole of alcohol and more
preferably the C.sub.15 -C.sub.20 primary alcohol ethoxylates containing
from 20-100 moles of ethylene oxide per mole of alcohol.
Other preferred binders include certain polymeric materials.
Polyvinylpyrrolidones with an average molecular weight of from 12,000 to
700,000 and polyethylene glycols (PEG) with an average molecular weight of
from 600 to 5.times.10.sup.6 preferably 1000 to 400,000 most preferably
1000 to 10,000 are examples of such polymeric materials. Copolymers of
maleic anhydride with ethylene, methylvinyl ether or methacrylic acid, the
maleic anhydride constituting at least 20 mole percent of the polymer are
further examples of polymeric materials useful as binder agents. These
polymeric materials may be used as such or in combination with solvents
such as water, propylene glycol and the above mentioned C.sub.10 -C.sub.20
alcohol ethoxylates containing from 5-100 moles of ethylene oxide per
mole.
Further examples of binders include the C.sub.10 -C.sub.20 mono- and
diglycerol ethers and also the C.sub.10 -C.sub.20 fatty acids.
Cellulose derivatives such as methylcellulose, carboxymethylcellulose and
hydroxyethylcellulose, and homo- or co-polymeric polycarboxylic acids or
their salts are other examples of binders suitable for use herein.
One method for applying the coating material involves agglomeration.
Preferred agglomeration processes include the use of any of the organic
binder materials described hereinabove. Any conventional
agglomerator/mixer may be used including, but not limited to pan, rotary
drum and vertical blender types. Molten coating compositions may also be
applied either by being poured onto, or spray atomized onto a moving bed
of bleaching agent.
Other means of providing the required controlled release include mechanical
means for altering the physical characteristics of the bleach to control
its solubility and rate of release. Suitable protocols could include
compaction, mechanical injection, manual injection, and adjustment of the
solubility of the bleach compound by selection of particle size of any
particulate component.
Whilst the choice of particle size will depend both on the composition of
the particulate component, and the desire to meet the desired controlled
release kinetics, it is desirable that the particle size should be more
than 500 micrometers, preferably having an average particle diameter of
from 800 to 1200 micrometers.
Additional protocols for providing the means of controlled release include
the suitable choice of any other components of the detergent composition
matrix such that when the composition is introduced to the wash solution
the ionic strength environment therein provided enables the required
controlled release kinetics to be achieved.
Alkalinity System
The compositions preferably contain an alkalinity system containing sodium
silicate having an SiO.sub.2 :Na.sub.2 O ratio of from 1.8 to 3.0,
preferably from 1.8 to 2.4, most preferably 2.0, present preferably at a
level of less than 20%, preferably from 1% to 15%, most preferably from 3%
to 12% by weight of SiO.sub.2. The alkali metal silicate may be in the
form of either the anhydrous salt or a hydrated salt.
The alkalinity system also preferably contains sodium metasilicate, present
at a level of at least 0.4% SiO.sub.2 by weight. Sodium metasilicate has a
nominal SiO.sub.2 :Na.sub.2 O ratio of 1.0. The weight ratio of said
sodium silicate to said sodium metasilicate, measured as SiO.sub.2, is
preferably from 50:1 to 5:4, more preferably from 15:1 to 2:1, most
preferably from 10:1 to 5:2.
Heavy Metal Ion Sequestrant
The detergent compositions of the invention preferably contain as an
optional component a heavy metal ion sequestrant. By heavy metal ion
sequestrant it is meant herein components which act to sequester (chelate)
heavy metal ions. These components may also have calcium and magnesium
chelation capacity, but preferentially they show selectivity to binding
heavy metal ions such as iron, manganese and copper.
Heavy metal ion sequestrants are generally present at a level of from 0.005
% to 20%, preferably from 0.1% to 10%, more preferably from 0.25% to 7.5%
and most preferably from 0.5% to 5% by weight of the compositions. The
weight ratio of heavy metal ion sequestrant to ATCA is preferably from
1:20 to 20:1, more preferably from 1:10 to 10:1, most preferably from 5:1
to 1:5.
Heavy metal ion sequestrants, which are acidic in nature, having for
example phosphonic acid or carboxylic acid functionalities, may be present
either in their acid form or as a complex/salt with a suitable counter
cation such as an alkali or alkaline metal ion, ammonium, or substituted
ammonium ion, or any mixtures thereof. Preferably any salts/complexes are
water soluble. The molar ratio of said counter cation to the heavy metal
ion sequestrant is preferably at least 1:1.
Suitable heavy metal ion sequestrants for use herein include organic
phosphonates, such as the amino alkylene poly (alkylene phosphonates),
alkali metal ethane 1-hydroxy disphosphonates and nitrilo trimethylene
phosphonates. Preferred among the above species are diethylene triamine
penta (methylene phosphonate), ethylene diamine tri (methylene
phosphonate) hexamethylene diamine tetra (methylene phosphonate) and
hydroxy-ethylene 1,1 diphosphonate.
Other suitable heavy metal ion sequestrant for use herein include
nitrilotriacetic acid and polyaminocarboxylic acids such as
ethylenediaminotetracetic acid, ethylenetriamine pentacetic acid,
ethylenediamine disuccinic acid, ethylenediamine diglutaric acid,
2-hydroxypropylenediamine disuccinic acid or any salts thereof.
Especially preferred is ethylenediamine-N,N'-disuccinic acid (EDDS) or the
alkali metal, alkaline earth metal, ammonium, or substituted ammonium
salts thereof, or mixtures thereof. Preferred EDDS compounds are the free
acid form and the sodium or magnesium salt or complex thereof.
Organodiphosphonic Acid
The detergent compositions preferably contain an organodiphosphonic acid
component, incorporated preferably at a level of from 0.01% to 5%, more
preferably from 0.1% to 2% by weight of the compositions. The weight ratio
of organodiphosphonic acid to ATCA is preferably from 1:20 to 20:1, more
preferably from 10:1 to 1:10, most preferably from 1:5 to 5:1.
By organo diphosphonic acid it is meant herein an organo diphosphonic acid
which does not contain nitrogen as part of its chemical structure. This
definition therefore excludes the organo aminophosphonates, which however
may be included in compositions of the invention as heavy metal ion
sequestrant components.
The organo diphosphonic acid is preferably a C.sub.1 -C.sub.4 diphosphonic
acid, more preferably a C.sub.2 diphosphonic acid, such as ethylene
diphosphonic acid, or most preferably ethane 1-hydroxy-1,1-diphosphonic
acid (HEDP) and may be present in partially or fully ionized form,
particularly as a salt or complex.
Enzyme
Another optional ingredient useful in the compositions is one or more
enzymes. Preferred enzymatic materials include the commercially available
lipases, amylases, neutral and alkaline proteases, esterases, cellulases,
pectinases, lactases and peroxidases conventionally incorporated into
detergent compositions. Suitable enzymes are discussed in U.S. Pat. Nos.
3,519,570 and 3,533,139.
Preferred commercially available protease enzymes include those sold under
the tradenames Alcalase, Savinase, Primase, Durazym, and Esperase by Novo
Industries A/S (Denmark), those sold under the tradename Maxatase, Maxacal
and Maxapem by Gist-Brocades, those sold by Genencor International, and
those sold under the tradename Opticlean and Optimase by Solvay Enzymes.
Protease enzyme may be incorporated into the compositions in accordance
with the invention at a level of from 0.0001% to 4% active enzyme by
weight of the composition.
Preferred amylases include, for example, .alpha.-amylases obtained from a
special strain of B licheniformis, described in more detail in
GB-1,269,839 (Novo). Preferred commercially available amylases include for
example, those sold under the tradename Rapidase by Gist-Brocades, and
those sold under the tradename Termamyl and BAN by Novo Industries A/S.
Amylase enzyme may be incorporated into the composition in accordance with
the invention at a level of from 0.0001% to 2% active enzyme by weight of
the composition.
Lipolytic enzyme (lipase) may be present at levels of active lipolytic
enzyme of from 0.0001% to 2% by weight, preferably 0.001% to 1% by weight,
most preferably from 0.001% to 0.5% by weight of the compositions. The
lipase may be fungal or bacterial in origin. Lipase from chemically or
genetically modified mutants of these strains are also useful herein. A
preferred lipase is described in Granted European Patent, EP-B-0218272.
An especially preferred lipase herein is obtained by cloning the gene from
Humicola lanuginosa and expressing the gene in Aspergillus oryza, as host,
as described in European Patent Application, EP-A-0258 068, which is
commercially available from Novo Industries A/S, Bagsvaerd, Denmark, under
the trade name Lipolase. This lipase is also described in U.S. Pat. No.
4,810,414, Huge-Jensen et al, issued Mar. 7, 1989.
Enzyme Stabilizing System
Preferred enzyme-containing compositions herein may comprise from about
0.001% to about 10%, preferably from about 0.005% to about 8%, most
preferably from about 0.01% to about 6%, by weight of an enzyme
stabilizing system. The enzyme stabilizing system can be any stabilizing
system which is compatible with the detersive enzyme. Such stabilizing
systems can comprise calcium ion, boric acid, propylene glycol, short
chain carboxylic acid, boronic acid, chlorine bleach scavengers and
mixtures thereof. Such stabilizing systems can also comprise reversible
enzyme inhibitors, such as reversible protease inhibitors.
Clay Softening System
The detergent compositions where formulated for laundry usage may contain a
clay softening system comprising a clay mineral compound and optionally a
clay flocculating agent.
The clay mineral compound is preferably a smectite clay compound. Smectite
clays are disclosed in the U.S. Pat. Nos. 3,862,058, 3,948,790, 3,954,632
and 4,062,647. European Patents Nos. EP-A-299,575 and EP-A-313,146 in the
name of the Procter and Gamble Company describe suitable organic polymeric
clay flocculating agents.
Lime Soap Dispersant Compound
The compositions of the invention may contain a lime soap dispersant
compound, preferably present at a level of from 0.1% to 40% by weight,
more preferably 1% to 20% by weight, most preferably from 2% to 10% by
weight of the compositions.
A lime soap dispersant is a material that prevents the precipitation of
alkali metal, ammonium or amine salts of fatty acids by calcium or
magnesium ions. Preferred lime soap dispersant compounds are disclosed in
PCT Application No. W093/08877.
Suds Suppressing System
The compositions of the invention, when formulated for use in machine
washing compositions, preferably comprise a suds suppressing system
present at a level of from 0.01% to 15%, preferably from 0.05% to 10%,
most preferably from 0.1% to 5% by weight of the composition.
Suitable suds suppressing systems for use herein may comprise essentially
any known antifoam compound, including, for example silicone antifoam
compounds, 2-alkyl and alcanol antifoam compounds. Preferred suds
suppressing systems and antifoam compounds are disclosed in PCT
Application No. WO93/08876 and copending European Application No.
93870132.3.
Polymeric Dye Transfer Inhibiting Agents
The compositions herein may also comprise from 0.01% to 10%, preferably
from 0.05% to 0.5% by weight of polymeric dye transfer inhibiting agents.
The polymeric dye transfer inhibiting agents are preferably selected from
polyamine N-oxide polymers, copolymers of N-vinylpyrrolidone and
N-vinylimidazole, polyvinylpyrrolidonepolymers or combinations thereof.
a) Polyamine N-oxide polymers
Polyamine N-oxide polymers suitable for use herein contain units having the
following structure formula:
##STR21##
wherein P is a polymerisable unit, and
##STR22##
R are aliphatic, etoxylated aliphatics, aromatic, heterocyclic or alicyclic
groups or any combination thereof whereto the nitrogen of the N-O group
can be attached or wherein the nitrogen of the N-O group is part of these
groups.
The N-O group can be represented by the following general structures:
##STR23##
wherein R1, R2 and R3 are aliphatic groups, aromatic, heterocyclic or
alicyclic groups or combinations thereof, x or/and y or/and z is 0 or 1
and wherein the nitrogen of the N-O group can be attached or wherein the
nitrogen of the N-O group forms part of these groups. The N-O group can be
part of the polymerisable unit (P) or can be attached to the polymeric
backbone or a combination of both.
Suitable polyamine N-oxides wherein the N-O group forms part of the
polymerisable unit comprise polyamine N-oxides wherein R is selected from
aliphatic, aromatic, alicyclic or heterocyclic groups. One class of said
polyamine N-oxides comprises the group of polyamine N-oxides wherein the
nitrogen of the N-O group forms part of the R-group. Preferred polyamine
N-oxides are those wherein R is a heterocyclic group such as pyrridine,
pyrrole, imidazole, pyrrolidine, piperidine, quinoline, acridine and
derivatives thereof.
Other suitable polyamine N-oxides are the polyamine oxides whereto the N-O
group is attached to the polymerisable unit. A preferred class of these
polyamine N-oxides comprises the polyamine N-oxides having the general
formula (I) wherein R is an aromatic, heterocyclic or alicyclic groups
wherein the nitrogen of the N-O functional group is part of said R group.
Examples of these classes are polyamine oxides wherein R is a heterocyclic
compound such as pyridine, pyrrole, imidazole and derivatives thereof.
The polyamine N-oxides can be obtained in almost any degree of
polymerisation. The degree of polymerisation is not critical provided the
material has the desired water-solubility and dye-suspending power.
Typically, the average molecular weight is within the range of 500 to
1,000,000.
b) Copolymers of N-vinylpyrrolidone and N-vinylimidazole
Suitable herein are copolymers of N-vinylimidazole and N-vinylpyrrolidone
having an average molecular weight range of from 5,000 to 50,000. The
preferred copolymers have a molar ratio of N-vinylimidazole to
N-vinylpyrrolidone from 1 to 0.2.
c) Polyvinylpyrrolidone
The detergent compositions herein may also utilise polyvinylpyrrolidone
("PVP") having an average molecular weight of from 2,500 to 400,000.
Suitable polyvinylpyrrolidones are commercially available from ISP
Corporation, New York, N.Y. and Montreal, Canada under the product names
PVP K-15 (viscosity molecular weight of 10,000), PVP K-30 (average
molecular weight of 40,000), PVP K-60 (average molecular weight of
160,000), and PVP K-90 (average molecular weight of 360,000). PVP K-15 is
also available from ISP Corporation. Other suitable polyvinylpyrrolidones
which are commercially available from BASF Corporation include Sokalan HP
165 and Sokalan HP 12.
d) Polyvinyloxazolidone
The detergent compositions herein may also utilise polyvinyloxazolidones as
polymeric dye transfer inhibiting agents. Said polyvinyloxazolidones have
an average molecular weight of from 2,500 to 400,000.
e) Polyvinylimidazole
The detergent compositions herein may also utilise polyvinylimidazole as
polymeric dye transfer inhibiting agent. Said polyvinylimidazoles
preferably have an average molecular weight of from 2,500 to 400,000.
Optical Brightener
The detergent compositions herein particularly where formulated for laundry
usage also optionally contain from about 0.005% to 5% by weight of certain
types of hydrophilic optical brighteners.
Hydrophilic optical brighteners useful herein include those having the
structural formula:
##STR24##
wherein R.sub.1 is selected from anilino, N-2-bis-hydroxyethyl and
NH-2-hydroxyethyl; R.sub.2 is selected from N-2-bis-hydroxyethyl,
N-2-hydroxyethyl-N-methylamino, morphilino, chloro and amino; and M is a
salt-forming cation such as sodium or potassium.
When in the above formula, R.sub.1 is anilino, R.sub.2 is
N-2-bis-hydroxyethyl and M is a cation such as sodium, the brightener is
4,4',-bis[(4-anilino-6-(N-2-bis-hydroxyethyl)-s-triazine-2-yl)amino]-2,2'-
stilbenedisulfonic acid and disodium salt. This particular brightener
species is commercially marketed under the tradename Tinopal-UNPA-GX by
Ciba-Geigy Corporation. Tinopal-UNPA-GX is the preferred hydrophilic
optical brightener useful in the detergent compositions herein.
When in the above formula, R.sub.1 is anilino, R.sub.2 is
N-2-hydroxyethyl-N-2-methylamino and M is a cation such as sodium, the
brightener is
4,4'-bis[(4-anilino-6-(N-2-hydroxyethyl-N-methylamino)-s-triazine-2-yl)ami
no]2,2'-stilbenedisulfonic acid disodium salt. This particular brightener
species is commercially marketed under the tradename Tinopal 5BM-GX by
Ciba-Geigy Corporation.
When in the above formula, R.sub.1 is anilino, R.sub.2 is morphilino and M
is a cation such as sodium, the brightener is
4,4'-bis[(4-anilino-6-morphilino-s-triazine-2-yl)amino]2,2'-stilbenedisulf
onic acid, sodium salt. This particular brightener species is commercially
marketed under the tradename Tinopal AMS-GX by Ciba Geigy Corporation.
Cationic Fabric Softening Agents
Cationic fabric softening agents can also be incorporated into compositions
in accordance with the present invention. Suitable cationic fabric
softening agents include the water insoluble tertiary amines or dilong
chain amide materials as disclosed in GB-A-1 514 276 and EP-B-0 011 340.
Cationic fabric softening agents are typically incorporated at total levels
of from 0.5% to 15% by weight, normally from 1% to 5% by weight.
Other Optional Ingredients
Other optional ingredients suitable for inclusion in the compositions of
the invention include perfumes, colours and filler salts, with sodium
sulfate being a preferred filler salt.
pH of the Compositions
The detergent compositions used in the present invention are preferably not
formulated to have an unduly high pH, in preference having a pH measured
as a 1% solution in distilled water of from 8.0 to 12.5, more preferably
from 9.0 to 11.8, most preferably from 9.5 to 11.5.
Form of the Compositions
The detergent compositions used in this invention can be formulated in any
desirable form such as powders, granulates, pastes, liquids, gels, bars
and tablets, granular and tablet forms being preferred.
The bulk density of the granular detergent compositions in accordance with
the present invention is typically of at least 650 g/liter, more usually
at least 700 g/liter and more preferably from 800 g/liter to 1200 g/liter.
The particle size of the components of granular compositions in accordance
with the invention should preferably be such that no more that 5% of
particles are greater than 1.4 mm in diameter and not more than 5% of
particles are less than 0.15 mm in diameter.
Compacted solids may be manufactured using any suitable compacting process,
such as tabletting, briquetting or extrusion, preferably tabletting.
Preferably tablets are manufactured using a standard rotary tabletting
press using compression forces of from 5 to 13 KN/cm.sup.2, more
preferably from 5 to 11 KN/cm.sup.2 so that the compacted solid has a
minimum hardness of 176N to 275N, preferably from 195N to 245N, measured
by a C100 hardness test as supplied by I. Holland instruments. This
process may be used to prepare homogeneous or layered tablets of any size
or shape. Preferably tablets are symmetrical to ensure the uniform
dissolution of the tablet in the wash solution.
According to the present invention the compacted solid form detergent
composition may fmd utility in all types of automatic dish and laundry
washing machines including industrial and domestic machines.
Generally, if the compositions are in liquid form the liquid should be
thixotropic (ie; exhibit high viscosity when subjected to low stress and
lower viscosity when subjected to high stress), or at least have very high
viscosity, for example, of from 1,000 to 10,000,000 centipoise.
Machine Dishwashing Method
Any suitable methods for machine washing or cleaning soiled tableware,
particularly soiled silverware are envisaged.
A preferred machine dishwashing method comprises treating soiled articles
selected from crockery, glassware, hollowware, silverware and cutlery and
mixtures thereof, with an aqueous liquid having dissolved or dispensed
therein an effective amount of a machine dishwashing composition in accord
with the invention. By an effective amount of the machine dishwashing
composition it is meant from 8 g to 60 g of product dissolved or dispersed
in a wash solution of volume from 3 to 10 liters, as are typical product
dosages and wash solution volumes commonly employed in conventional
machine dishwashing methods.
Laundry Washing Method
Machine laundry methods herein typically comprise treating soiled laundry
with an aqueous wash solution in a washing machine having dissolved or
dispensed therein an effective amount of a machine laundry detergent
composition in accord with the invention. By an effective amount of the
detergent composition it is meant from 40 g to 300 g of product dissolved
or dispersed in a wash solution of volume from 5 to 65 liters, as are
typical product dosages and wash solution volumes commonly employed in
conventional machine laundry methods.
In a preferred use aspect a dispensing device is employed in the washing
method. The dispensing device is charged with the detergent product, and
is used to introduce the product directly into the drum of the washing
machine before the commencement of the wash cycle. Its volume capacity
should be such as to be able to contain sufficient detergent product as
would normally be used in the washing method.
Once the washing machine has been loaded with laundry the dispensing device
containing the detergent product is placed inside the drum. At the
commencement of the wash cycle of the washing machine water is introduced
into the drum and the drum periodically rotates. The design of the
dispensing device should be such that it permits containment of the dry
detergent product but then allows release of this product during the wash
cycle in response to its agitation as the drum rotates and also as a
result of its contact with the wash water.
To allow for release of the detergent product during the wash the device
may possess a number of openings through which the product may pass.
Alternatively, the device may be made of a material which is permeable to
liquid but impermeable to the solid product, which will allow release of
dissolved product. Preferably, the detergent product will be rapidly
released at the start of the wash cycle thereby providing transient
localised high concentrations of product in the drum of the washing
machine at this stage of the wash cycle.
Preferred dispensing devices are reusable and are designed in such a way
that container integrity is maintained in both the dry state and during
the wash cycle. Especially preferred dispensing devices for use with the
composition of the invention have been described in the following patents;
GB-B-2, 157, 717, GB-B-2, 157, 718, EP-A-0201376, EP-A-0288345 and
EP-A-0288346. An article by J. Bland published in Manufacturing Chemist,
November 1989, pages 41-46 also describes especially preferred dispensing
devices for use with granular laundry products which are of a type
commonly know as the "granulette". Another preferred dispensing device for
use with the compositions of this invention is disclosed in PCT Patent
Application No. WO94/11562.
Especially preferred dispensing devices are disclosed in European Patent
Application Publication Nos. 0343069 & 0343070. The latter Application
discloses a device comprising a flexible sheath in the form of a bag
extending from a support ring defining an orifice, the orifice being
adapted to admit to the bag sufficient product for one washing cycle in a
washing process. A portion of the washing medium flows through the orifice
into the bag, dissolves the product, and the solution then passes
outwardly through the orifice into the washing medium. The support ring is
provided with a masking arrangement to prevent egress of wetted,
undissolved, product, this arrangement typically comprising radially
extending walls extending from a central boss in a spoked wheel
configuration, or a similar structure in which the walls have a helical
form.
Alternatively, the dispensing device may be a flexible container, such as a
bag or pouch. The bag may be of fibrous construction coated with a water
impermeable protective material so as to retain the contents, such as is
disclosed in European published Patent Application No. 0018678.
Alternatively it may be formed of a water-insoluble synthetic polymeric
material provided with an edge seal or closure designed to rupture in
aqueous media as disclosed in European published Patent Application Nos.
0011500, 0011501, 0011502, and 0011968. A convenient form of water
frangible closure comprises a water soluble adhesive disposed along and
sealing one edge of a pouch formed of a water impermeable polymeric film
such as polyethylene or polypropylene.
EXAMPLES
Abbreviations Used in Examples
In the detergent compositions, the abbreviated component identifications
have the following meanings:
LAS: Sodium linear C.sub.12 alkyl benzene sulfonate
TAS: Sodium tallow alkyl sulfate
C45AS: Sodium C.sub.14 -C.sub.15 linear alkyl sulfate
CxyEzS: Sodium C.sub.1x -C.sub.1y branched alkyl sulfate condensed with z
moles of ethylene oxide
C45E7: A C.sub.14-15 predominantly linear primary alcohol condensed with an
average of 7 moles of ethylene oxide
C25E3: A C.sub.14-15 branched primary alcohol condensed with an average of
3 moles of ethylene oxide
C25E5: A C.sub.12-15 branched primary alcohol condensed with an average of
5 moles of ethylene oxide
CEQ: R.sub.1 COOCH.sub.2 CH.sub.2.N.sup.+ (CH.sub.3).sub.3 with R.sub.1
=C.sub.11 -C.sub.13
QAS: R.sub.2.N.sup.+ (CH.sub.3).sub.2 (C.sub.2 H.sub.4 OH with R.sub.2
=C.sub.12 -C.sub.14
Soap: Sodium linear alkyl carboxylate derived from an 80/20 mixture of
tallow and coconut oils
TFAA: C.sub.16 -C.sub.18 alkyl N-methyl glucamide
TPKFA: C.sub.12 -C.sub.14 topped whole cut fatty acids
Zeolite A: Hydrated Sodium Aluminosilicate of formula Na.sub.12 (AlO.sub.2
SiO.sub.2).sub.12.27H.sub.2 O having a primary particle size in the range
from 0.1 to 10 micrometers
Zeolite MAP: Hydrated sodium aluminosilicate MAP having a silicon to
aluminium ratio of 1.07:1.
NaSKS-6: Crystalline layered silicate of formula .gamma.-Na.sub.2 Si.sub.2
O.sub.5
Citric Acid: Anhydrous citric acid
Bicarbonate: Anhydrous sodium bicarbonate with a particle size distribution
between 400 .mu.m and 1200 .mu.m
MA/AA: Copolymer of 1:4 maleic/acrylic acid, average molecular weight about
70,000
CMC: Sodium carboxymethyl cellulose
Alcalase: Proteolytic enzyme of activity 3AU/g sold by NOVO Industries A/S
Cellulase: Cellulytic enzyme of activity 1000 CEVU/g sold by NOVO
Industries A/S under the tradename Carezyme
Lipase: Lipolytic enzyme of activity 100kLU/g sold by NOVO Industries A/S
under the tradename Lipolase
Endolase: Endoglucase enzyme of activity 3000 CEVU/g sold by NOVO
Industries A/S
Photoactivated bleach: Sulfonated Zinc Phythlocyanine encapsulated in
dextrin soluble polymer
Brightener 1: Disodium 4,4'-bis(2-sulphostyryl)biphenyl
Brightener 2: Disodium 4,4'-bis
(4-anilino-6-morpholino-1.3.5-triazin-2-yl)amino)
stilbene-2:2'-disulfonate
PVNO: Polyvinylpyridine N-oxide
PVPVI: Copolymer of polyvinylpyrolidone and vinylimidazole
SRP 1: Sulfobenzoyl end capped esters with oxyethylene oxy and terephtaloyl
backbone
SRP 2: Diethoxylated poly (1,2 propylene terephtlate) short block polymer
Silicone antifoam: Polydimethylsiloxane foam controller with
siloxane-oxyalkylene copolymer as dispersing agent with a ratio of said
form controller to said dispersing agent of 10:1 to 100:1
NOBS: Nonanoyloxybenzene sulfonate in the form of the sodium salt
STPP: Sodium tripolyphosphate
MGDA: Methyl Glycine Diacetic acid
Citrate: Tri-sodium citrate dihydrate
Carbonate: Anhydrous sodium carbonate
Silicate: Amorphous Sodium Silicate (SiO.sub.2 :Na.sub.2 O ratio=2.0)
Metasilicate: Sodium metasilicate (SiO.sub.2 : Na.sub.2 O ratio=1.0)
PB1: Anhydrous sodium perborate monohydrate
PB4: Sodium perborate tetrahydrate of nominal formula NaBO.sub.2.3H.sub.2
O.H.sub.2 O.sub.2
Percarbonate: Anhydrous sodium percarbonate of nominal formula 2.Na.sub.2
CO.sub.3.3H.sub.2 O.sub.2
Nonionic: C.sub.13 -C.sub.15 mixed ethoxylated/propoxylated fatty alcohol
with an average degree of ethoxylation of 3.8 and an average degree of
propoxylation of 4.5 sold under the tradename Plurafac LF404 by BASF GmbH
(low foaming)
TAED: Tetraacetyl ethylene diamine
HEDP: Ethane 1-hydroxy-1,1-diphosphonic acid
DETPMP: Diethyltriamine penta (methylene) phosphonate, marketed by monsanto
under the tradename Dequest 2060
PAAC: Pentaamine acetate cobalt (III) salt
BzP: Benzoyl Peroxide
Paraffin: Paraffm oil sold under the tradename Winog 70 by Wintershall.
Protease: Proteolytic enzyme of activity 4KNPUI/g sold under the tradename
Savinase by Novo Industries A/S
Amylase: Amylolytic enzyme of activity 60KNU/g sold under tradename
Termamyl 60T by Novo Industries A/S
BTA: Benzotriazole
Bismuth nitrate: Bismuth nitrate salt
PA30: Polyacrylic acid of average molecular weight approximately 8,000
Terpolymer: Terpolymer of average molecular weight approx. 7,000,
comprising acrylic:maleic:ethylacrylic acid monomer units at a weight
ratio of 60:20:20
480N: Random copolymer of 3:7 acrylic/methacrylic acid, average molecular
weight about 3,500
Sulphate: Arihydrous sodium sulphate.
NaDCC: Sodium dichloroisocyanurate
KOH: 100% active solution of Potassium Hydroxide
BSA: Amylotic enzyme sold under the tradename LE17 by Novo Industries A/S
(approx 1% enzyme activity)
pH: Measured as a 1% solution in distilled water at 20.degree. C.
In the following examples all levels are quoted as % by weight of the
composition:
Example 1
The following compact high density (0.96 Kg/l) dishwashing detergent
compositions A to F were prepared in accord with the invention.
______________________________________
A B C D E F
______________________________________
STPP 24.80 24.80 25.00
28.39 28.50
20.00
Citrate -- -- -- -- 10.00 10.00
Carbonate -- -- 17.50 17.50 -- --
MGDA 1.0 2.50 2.00 2.00 3.00 2.00
Silicate 20.36 20.36 14.81 14.81 14.81 --
Metasilicate 2.50 2.50 2.50 -- -- --
PB1 7.79 7.79 9.74 14.28 9.74 --
PB4 -- -- -- -- -- --
Percarbonate -- -- -- -- -- 6.70
Non-ionic 1.50 1.50 2.00 1.50 2.00 2.60
TAED 2.39 2.39 2.39 -- -- 4.00
HEDP 0.46 0.46 1.00 -- 0.83 --
DETPMP -- -- 0.65 -- -- --
PAAC -- -- -- 0.20 -- --
BzP -- -- -- 4.44 -- --
Paraffin 0.50 0.50 0.50 0.50 -- 0.20
Protease 2.20 2.20 2.20 2.20 2.00 0.50
Amylase 1.50 1.50 1.20 1.50 1.00 1.10
BTA 0.30 0.30 0.30 0.30 -- --
Bismuth Nitrate -- -- 0.30 -- -- --
PA30 -- -- -- -- -- 3.0
Terpolymer -- -- -- 4.00 -- --
480N 2.77 2.77 6.00 -- 6.67 3.0
Sulphate 8.44 8.44 20.77 -- 23.24 1.00
Misc inc moisture
to balance
pH (1% solution) 10.90 10.90 11.00 10.80 10.90 9.60
______________________________________
Example 2
The following granular dishwashing detergent compositions examples G to L
of bulk density 1.02 Kg/L were prepared in accord with the invention:
______________________________________
G H I J K L
______________________________________
STPP 30.00 30.00 30.00
27.90 34.50
26.70
Carbonate 30.50 23.50 30.50 23.00 30.50 2.80
MGDA 2.00 2.00 2.00 5.00 5.00 2.00
Silicate 7.40 7.40 7.40 12.00 8.00 18.34
PB1 4.40 4.40 4.40 -- 4.40 --
NaDCC -- -- -- 2.00 -- 1.50
Nonionic 0.75 0.75 0.75 1.90 1.20 0.50
TAED 1.00 1.00 -- -- 1.00 --
PAAC -- -- 0.004 -- -- --
BzP -- 1.40 -- -- -- --
Paraffin 0.25 0.25 0.25 -- -- --
Protease 1.10 1.10 1.10 -- 2.20 --
Amylase 0.38 0.38 0.38 -- 0.80 --
BTA 0.15 -- 0.15 -- -- --
480N 3.00 3.50 4.00 5.25 6.67 6.00
Sulphate 23.90 21.90 21.90 26.40 12.40 --
Misc inc moisture
to balance
pH (1% solution) 10.80 10.80 10.80 10.70 10.70 12.30
______________________________________
Example 3
The following detergent composition tablets in accord with the present
invention of 25 g weight were prepared by compression of a granular
dishwashing detergent composition at a pressure of 13 KN/cm.sup.2 using a
standard 12 head rotary press:
______________________________________
M N O
______________________________________
STPP 45.00 38.80 32.50
Citrate -- -- 15.00
Carbonate -- 5.00 --
MGDA 2.00 4.00 2.00
Silicate 26.40 14.80 25.00
Protease 1.76 2.20 0.60
Amylase 1.20 -- 0.60
PB1 1.56 7.79 --
PB4 6.92 -- 11.40
Nonionic 1.20 2.00 1.10
TAED 4.33 2.39 0.80
HEDP 0.67 0.67 --
DETPMP 0.65 -- --
Paraffin 0.42 0.50 --
BTA 0.24 0.30 --
PA30 3.2 3.2 3.2
Sulphate 25.05 12.70 1.20
Misc inc moisture to balance
pH (1% solution) 10.60 10.60 11.00
______________________________________
Example 4
The following liquid detergent compositions in accord with the present
invention P to Q, of density 1.40 Kg/L were prepared:
______________________________________
P Q
______________________________________
STPP 31.30 18.00
Carbonate 2.70 2.00
MGDA 2.00 2.00
Silicate -- 4.40
NaDCC 1.10 1.15
Nonionic 2.50 1.00
Paraffin 2.20 --
Protease 0.60 0.50
Amylase 0.80 0.40
480N 0.50 4.00
KOH -- 6.00
Sulphate 1.60 --
Misc inc moisture to balance
pH (1% solution) 9.10 10.00
______________________________________
Example 5
The following granular laundry detergent compositions A' to C' of bulk
density 750 g/liter were prepared in accord with the invention:
______________________________________
A' B' C'
______________________________________
LAS 5.25 5.61 4.76
TAS 1.25 1.86 1.57
C45AS -- 2.24 3.89
C25AE3S -- 0.76 1.18
C45E7 3.25 -- 5.0
C25E3 -- 5.5 --
CEQ 0.8 2.0 2.0
STPP 19.7 19.5 19.5
MGDA 0.2 0.3 10.0
Zeolite A -- -- 19.5
Zeolite MAP -- 19.5 --
NaSKS-6/citric acid -- 10.6 10.6
(79:21)
Carbonate 6.1 21.4 21.4
Bicarbonate -- 2.0 2.0
Silicate 6.8 -- --
Sodium sulfate 39.8 -- 14.3
PB4 5.0 12.7 --
TAED 0.5 3.1 --
DETPMP 0.25 0.2 0.2
HEDP -- 0.3 0.3
Protease 0.26 0.85 0.85
Lipase 0.15 0.15 0.15
Cellulase 0.28 0.28 0.28
Amylase 0.1 0.1 0.1
PA30 0.8 1.6 1.6
CMC 0.2 0.4 0.4
Photoactivated bleach 15 27 27
(ppm) ppm ppm ppm
Brightener 1 0.08 0.19 0.19
Brightener 2 -- 0.04 0.04
Perfume 0.3 0.3 0.3
Silicone antifoam 0.5 2.4 2.4
Minors/misc to 100%
______________________________________
Example 6
The following detergent formulations, according to the present invention
were prepared:
______________________________________
D' E' F'
______________________________________
Blown Powder
STPP 24.0 -- 24.0
Zeolite A -- 24.0 --
MGDA 0.1 0.5 2.0
C45AS 9.0 6.0 13.0
PA30 2.0 4.0 2.0
LAS 6.0 8.0 11.0
TAS 2.0 -- --
Silicate 7.0 3.0 3.0
CMC 1.0 1.0 0.5
Brightener 2 0.2 0.2 0.2
Soap 1.0 1.0 1.0
DTPMP 0.4 0.4 0.2
Spray On
C45E7 2.5 2.5 2.0
C25E3 2.5 2.5 2.0
Silicone antifoam 0.3 0.3 0.3
Perfume 0.3 0.3 0.3
Dry additives
Carbonate 6.0 13.0 15.0
PB4 18.0 18.0 10.0
PB1 4.0 4.0 0
TAED 3.0 3.0 1.0
Photoactivated bleach 0.02 0.02 0.02
Protease 1.0 1.0 1.0
Lipase 0.4 0.4 0.4
Amylase 0.25 0.30 0.15
Dry mixed sodium 3.0 3.0 5.0
sulfate
Balance (Moisture & 100.0 100.0 100.0
Miscellaneous)
Density (g/liter) 630 670 670
______________________________________
Example 7
The following nil bleach-containing detergent formulations of particular
use in the washing of colored clothing, according to the present invention
were prepared:
______________________________________
G' H'
______________________________________
Blown Powder
STPP 15.0 15.0
MGDA 0.2 2.0
Sodium sulfate 0.0 5.0
LAS 3.0 3.0
DTPMP 0.4 0.5
CMC 0.4 0.4
PA30 4.0 4.0
Agglomerates
C45AS -- --
LAS 6.0 5.0
TAS 3.0 2.0
Silicate 4.0 4.0
Zeolite A 10.0 15.0
CMC -- --
MA/AA -- --
Carbonate 9.0 7.0
Spray On
Perfume 0.3 0.3
C45E7 4.0 4.0
C25E3 2.0 2.0
Dry additives
MA/AA -- --
NaSKS-6 -- --
Citrate 10.0 --
Bicarbonate 7.0 3.0
Carbonate 8.0 5.0
PVPVI/PVNO 0.5 0.5
Alcalase 0.5 0.3
Lipase 0.4 0.4
Amylase 0.6 0.6
Cellulase 0.6 0.6
Silicone antifoam 5.0 5.0
Dry additives
Sodium sulfate 0.0 9.0
Balance (Moisture and 100.0 100.0
Miscellaneous)
Density (g/liter) 700 700
______________________________________
Example 8
The following detergent formulations, according to the present invention
were prepared:
______________________________________
I' J' K' L'
______________________________________
LAS 20.0 14.0 24.0 22.0
QAS 0.7 1.0 -- 0.7
TFAA -- 1.0 -- --
C25E5/C45E7 -- 2.0 -- 0.5
C45E3S -- 2.5 -- --
STPP 30.0 18.0 30.0 22.0
Silicate 9.0 5.0 10.0 8.0
Carbonate 13.0 7.5 -- 5.0
MGDA 0.2 1.0 2.0 2.0
Bicarbonate -- 7.5 -- --
DTPMP 0.7 1.0 -- --
SRP 1 0.3 0.2 -- 0.1
PA30 2.0 1.5 2.0 1.0
CMC 0.8 0.4 0.4 0.2
Protease 0.8 1.0 0.5 0.5
Amylase 0.8 0.4 -- 0.25
Lipase 0.2 0.1 0.2 0.1
Cellulase 0.15 0.05 -- --
Photoactivated 70 45 -- 10
bleach (ppm) ppm ppm ppm
Brightener 1 0.2 0.2 0.08 0.2
PB1 6.0 2.0 -- --
NOBS 2.0 1.0 -- --
Balance 100 100 100 100
(Moisture and
Miscellaneous)
______________________________________
Example 9
The following detergent formulations, according to the present invention
were prepared:
______________________________________
M' N' O'
______________________________________
Blown Powder
STPP 30.0 22.0 6.0
MGDA 2.0 2.0 2.0
Sodium sulfate 19.0 5.0 7.0
PA30 3.0 3.0 6.0
LAS 14.0 12.0 22.0
C45AS 8.0 7.0 7.0
Silicate -- 1.0 5.0
Soap -- -- 2.0
Brightener 1 0.2 0.2 0.2
Carbonate 8.0 16.0 20.0
DTPMP -- 0.4 0.4
Spray On
C45E7 1.0 1.0 1.0
Dry additives
PVPVI/PVNO 0.5 0.5 0.5
Protease 1.0 1.0 1.0
Lipase 0.4 0.4 0.4
Amylase 0.1 0.1 0.1
Cellulase 0.1 0.1 0.1
NOBS -- 6.1 4.5
PB1 1.0 5.0 6.0
Sodium sulfate -- 6.0 --
Balance (Moisture 100 100 100
and Miscellaneous)
______________________________________
Example 10
The following high density and bleach-containing detergent formulations,
according to the present invention were prepared:
______________________________________
P' Q' R'
______________________________________
Blown Powder
STPP 15.0 15.0 15.0
MGDA 2.0 2.0 2.0
Sodium sulfate 0.0 5.0 0.0
LAS 3.0 3.0 3.0
QAS -- 1.5 1.5
DTPMP 0.4 0.4 0.4
CMC 0.4 0.4 0.4
PA30 4.0 2.0 2.0
Agglomerates
LAS 5.0 5.0 5.0
TAS 2.0 2.0 1.0
Silicate 3.0 3.0 4.0
Zeolite A 8.0 8.0 8.0
Carbonate 8.0 8.0 4.0
Spray On
Perfume 0.3 0.3 0.3
C45E7 2.0 2.0 2.0
C25E3 2.0 -- --
Dry additives
Citrate 5.0 -- 2.0
Bicarbonate -- 3.0 --
Carbonate 8.0 15.0 10.0
TAED 6.0 2.0 5.0
PB1 14.0 7.0 10.0
Polyethylene oxide of MW -- -- 0.2
5,000,000
Bentonite clay -- -- 10.0
Protease 1.0 1.0 1.0
Lipase 0.4 0.4 0.4
Amylase 0.6 0.6 0.6
Cellulase 0.6 0.6 0.6
Silicone antifoam 5.0 5.0 5.0
Dry additives
Sodium sulfate 0.0 3.0 0.0
Balance (Moisture and 100.0 100.0 100.0
Miscellaneous)
Density (g/liter) 850 850 850
______________________________________
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